bluuebunny/crossref_metadata_2025 huggingface dataset:
Transfer Hydrosilylation
Authors: Oestreich Martin
Published: November 2015

Transfer hydrogenation is without question a common technology in industry and academia. Unlike its countless varieties, conceptually related transfer hydrosilylations had essentially been unreported until the recent development of a radical and an ionic variant. The new methods are both based on a silicon‐substituted cyclohexa‐1,4‐diene and hinge on the aromatization of the corresponding cyclohexadienyl radical and cation intermediates, respectively, concomitant with homo‐ or heterolytic fission of the SiC bond. Both the radical and ionic transfer hydrosilylation are brought into context with one other in this Minireview, and early insight into the possibility of transfer hydrosilylation is included. Although the current state‐of‐the‐art is certainly still limited, the recent advances have already revealed the promising potential of transfer hydrosilylation.
Production of New Cladosporin Analogues by Reconstitution of the Polyketide Synthases Responsible for the Biosynthesis of this Antimalarial Agent
Authors: Cochrane Rachel V. K. , Sanichar Randy , Lambkin Gareth R. , Reiz Béla , Xu Wei , Tang Yi , Vederas John C.
Published: November 2015

The antimalarial agent cladosporin is a nanomolar inhibitor of the Plasmodium falciparum lysyl‐tRNA synthetase, and exhibits activity against both blood‐ and liver‐stage infection. Cladosporin can be isolated from the fungus Cladosporium cladosporioides, where it is biosynthesized by a highly reducing (HR) and a non‐reducing (NR) iterative type I polyketide synthase (PKS) pair. Genome sequencing of the host organism and subsequent heterologous expression of these enzymes in Saccharomyces cerevisiae produced cladosporin, confirming the identity of the putative gene cluster. Incorporation of a pentaketide intermediate analogue indicated a 5+3 assembly by the HR PKS Cla2 and the NR PKS Cla3 during cladosporin biosynthesis. Advanced‐intermediate analogues were synthesized and incorporated by Cla3 to furnish new cladosporin analogues. A putative lysyl‐tRNA synthetase resistance gene was identified in the cladosporin gene cluster. Analysis of the active site emphasizes key structural features thought to be important in resistance to cladosporin.
Building Giant Carbocycles by Reversible C−C Bond Formation
Authors: Beaudoin Daniel , Levasseur‐Grenon Olivier , Maris Thierry , Wuest James D.
Published: November 2015

We describe a simple way to build giant macrocyclic hydrocarbons by the reversible formation of carbon–carbon bonds. Specifically, extended spirobifluorene‐substituted derivatives of Wittig's hydrocarbon were synthesized and found to undergo oligomerization, giving the largest hydrocarbon that has been crystallized and characterized by X‐ray diffraction to date.
Ultrathin Co3O4 Layers Realizing Optimized CO2 Electroreduction to Formate
Authors: Gao Shan , Jiao Xingchen , Sun Zhongti , Zhang Wenhua , Sun Yongfu , Wang Chengming , Hu Qitao , Zu Xiaolong , Yang Fan , Yang Shuyang , Liang Liang , Wu Ju , Xie Yi
Published: November 2015

Electroreduction of CO2 into hydrocarbons could contribute to alleviating energy crisis and global warming. However, conventional electrocatalysts usually suffer from low energetic efficiency and poor durability. Herein, atomic layers for transition‐metal oxides are proposed to address these problems through offering an ultralarge fraction of active sites, high electronic conductivity, and superior structural stability. As a prototype, 1.72 and 3.51 nm thick Co3O4 layers were synthesized through a fast‐heating strategy. The atomic thickness endowed Co3O4 with abundant active sites, ensuring a large CO2 adsorption amount. The increased and more dispersed charge density near Fermi level allowed for enhanced electronic conductivity. The 1.72 nm thick Co3O4 layers showed over 1.5 and 20 times higher electrocatalytic activity than 3.51 nm thick Co3O4 layers and bulk counterpart, respectively. Also, 1.72 nm thick Co3O4 layers showed formate Faradaic efficiency of over 60 % in 20 h.
Oil sorbers based on renewable sources and coffee grounds
Authors: Marques Fernanda D. , Souza Fernando G. , Oliveira Geiza E.
Published: November 2015

This work presents useful composites for oil spill cleanup processes. These systems are composed of a polyester matrix loaded with coffee ground powder and maghemite. They were prepared by in situ polymerization. The aliphatic monomers proportion—castor oil and glycerin—was studied with the aim of understanding the effect of feed ratio on the product properties. The materials were studied using several techniques, including Fourier Transform Infrared Spectroscopy, Ultraviolet‐visible Spectrophotometry, and Wide Angle X‐ray Scattering, with magnetic force tests used for the characterization of materials. Density tests showed the presence of coffee grounds causes an important reduction in the density values of composites, improving their flotation. The interaction between composites and petroleum is more than twice that between composites and water. Moreover, for all magnetizable composites, the removal capability was (25.1 ± 1.2) g/g (petroleum/composite), allowing us to state that this is a promising material for use in oil spill cleanup processes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43127.
Switchable surfaces from highly hydrophobic to highly hydrophilic using covalent imine bonds
Authors: Godeau Guilhem , Darmanin Thierry , Guittard Frédéric
Published: November 2015

The formation of materials with switchable wettability is extremely important for various applications such as in separation membranes or liquid transportation. Here, we report for the first time the use of imine bonds in order to prepare switchable hydrophobic/hydrophilic surfaces. Based on a poly(3,4‐ethylenedioxythiophene) surface bearing amino groups, imination reaction allows for reversible functionalization of surfaces with various carbonyl groups. Here, surfaces functionalization induces high hydrophobic properties while the surface structures are preserved. This reaction can be a choice method to prepare switchable surfaces for a large range of applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43130.
Emulsifier‐free poly[2‐(diethylamino)ethyl methacrylate] microgels with cationic quaternary ammonium monomers
Authors: Karabacak R. Bengü
Published: November 2015

Although poly[2‐(diethylamino)ethyl methacrylate] (PDEA) microgels are biocompatible and show potential in drug delivery, little research exists with respect to their preparation. Therefore, emulsifier‐free PDEA microgels were synthesized in the presence of cationic ammonium salts of 2‐(dimethylamino)ethyl methacrylate (DMA) that were quaternized with 1‐bromohexadecane, 1‐bromooctadecane, 1‐bromopentane, or benzyl chloride. These served as both comonomers and polymerizable surfactants, providing colloidal stability to the DEA droplets during polymerization. The stability of the microgel particles in different pH values between 4 and 11 was investigated by turbidity–wavelength measurements. The benzyl group containing monomer was the most stabilizing. The pH‐responsive behavior of the microgels in dilute aqueous solution was examined with respect to the amount of DEA, amount of copolymer, type of copolymer, and water content. Most of the microgels remain colloidally stable up to a pH of 9.0, while particles are less than 300 nm in size at pH 8.0. The isoelectric points of the microgels are higher than 8.5 in most cases. In fact, this value exceeds 12.0 by modifying the amount of copolymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43196.
Histological Development of the Immune Tissues of a Marsupial, the Red‐Tailed Phascogale (Phascogale calura)
Authors: Borthwick Casey R. , Old Julie M.
Published: November 2015

Red‐tailed phascogale (Phascogale calura) pouch young at birth were relatively underdeveloped in comparison with their eutherian counterparts, and the lymphoid tissues of the immune system were found to be histologically immature. The phascogale thymus rapidly developed in the first few days of pouch life and was quickly populated with lymphocytes. By the end of pouch life, involution of the thymus was underway. The bone marrow started to develop in the early stage of pouch life, although adipocytes and megakaryocytes were not observed until slightly later. The liver was hematopoietic from birth and reached histological maturity toward the end of pouch life. The lymph nodes were difficult to detect macroscopically because of their small size, but were easily identified microscopically later in pouch life, particularly in the mesentery, and these lymph nodes exhibited germinal centers by the end of pouch life. The early spleen was predominately mesenchymal, but exhibited some erythropoiesis. Follicles with well‐developed germinal centers were not observed until the latest stage of pouch life. Although intraepithelial lymphocytes were detected in the intestines early in pouch life, the discrete lymphoid aggregates and Peyer's patches characteristic of the gut‐associated lymphoid tissue (GALT) were not detected until later in pouch life. This is the first report of histological development in phascogale pouch young, as well as the first report of the thymus, bone marrow, and lymph nodes in this dasyurid species at any age. Anat Rec, 299:207–219, 2016. © 2015 Wiley Periodicals, Inc.
Blue emitting ZnO nanostructures grown through cellulose bio‐templates
Authors: Oudhia Anjali , Sharma Savita , Kulkarni Pragya , Kumar Rajesh
Published: November 2015

This paper presents a green and cost‐effective recipe for the synthesis of blue‐emitting ZnO nanoparticles (NPs) using cellulose bio‐templates. Azadirachta indica (neem) leaf extract prepared in different solvents were used as biological templates to produce nanostructures of wurtzite ZnO with a particle size ~12–36 nm. A cellulose‐driven capping mechanism is used to describe the morphology of ZnO NPs. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), Fourier transform infra‐red (FTIR) and photoluminescence (PL) studies showed that solvents affect the growth process and the capping mechanism of bio‐template severely. Structural changes in ZnO NPs were evident with variation in pH, dielectric constants (DC) and boiling points (BP) of solvents. Furthermore, an energy band model is proposed to explain the origin of the blue emission in the as‐obtained ZnO NPs. PL excitation studies and the theoretical enthalpy values of individual defects were used to establish the association between the interstitial‐zinc‐related defect levels and the blue emission. Copyright © 2015 John Wiley & Sons, Ltd.
Characterization of the binding of paylean and DNA by fluorescence, UV spectroscopy and molecular docking techniques
Authors: Zhou Huifeng , Bi Shuyun , Wang Yu , Zhao Tingting
Published: November 2015

The interaction of paylean (PL) with calf thymus DNA (ctDNA) was investigated using fluorescence spectroscopy, UV absorption, melting studies, ionic strength, viscosity experiments and molecular docking under simulated physiological conditions. Values for the binding constant Ka between PL and DNA were 5.11 × 103, 2.74 × 103 and 1.74 × 103 L mol–1 at 19, 29 and 39°C respectively. DNA quenched the intrinsic fluorescence of PL via a static quenching procedure as shown from Stern–Volmer plots. The relative viscosity and the melting temperature of DNA were basically unchanged in the presence of PL. The fluorescence intensity of PL–DNA decreased with increasing ionic strength. The value of Ka for PL with double‐stranded DNA (dsDNA) was larger than that for PL with single‐stranded DNA (ssDNA). All the results revealed that the binding mode was groove binding, and molecular docking further indicated that PL was preferentially bonded to A–T‐rich regions of DNA. The values for ΔH, ΔS and ΔG suggested that van der Waals forces or hydrogen bonding might be the main acting forces between PL and DNA. The binding distance was determined to be 3.37 nm based on the theory of Förster energy transference, which indicated that a non‐radiation energy transfer process occurred. Copyright © 2015 John Wiley & Sons, Ltd.
Reaction of 1,2‐Difunctionalized Ethanes with Aryl Iodides in Copper‐catalyzed Cross‐Coupling: Application to Synthesis of Phenols
Authors: Kim Jihye , Battsengel Oyunsaikhan , Liu Yajun , Chae Junghyun
Published: November 2015

A series of 1,2‐difunctionalized ethanes, such as ethylene glycol, 2‐aminoethanol, 1,2‐diaminoethane, 2‐dimethylaminoethanol, N′,N′‐dimethylethane‐1,2‐diamine, were investigated to test the reactivity with aryl iodides in the presence of copper catalysts. Under the reaction conditions, they produce the various C‐heteroatom cross‐coupled products. Interestingly, ethylene glycol and 2‐dimethylaminoethanol afforded mainly the phenolic compounds while the others produced different cross‐coupled products. Although ethylene glycol and 2‐dimethylaminoethanol resulted in the same product, their behaviors in the reaction were quite different: ethylene glycol appears to mostly act as the ligand and 2‐dimethylaminoethanol appears to serve as both the ligand and reactant. This finding led to a copper‐catalyzed synthesis of phenols using either ethylene glycol or 2‐dimethylaminoethanol, which can be applied to a variety of aryl iodides, providing an alternative synthetic route to phenols
Simultaneous Determination of Nonsteroidal Anti‐Inflammatory Drugs in Aqueous Samples Using Dispersive Liquid–Liquid Microextraction and HPLC Analysis
Authors: Park So Yeon , Myung Seung‐Woon
Published: November 2015

A simple, effective, and environmentally friendly sample preparation method was developed by using dispersive liquid–liquid microextraction prior to high‐performance liquid chromatography analysis for the extraction/concentration and assay of nonsteroidal anti‐inflammatory drugs (NSAIDs), including indoprofen, ketoprofen, naproxen, diclofenac, ibuprofen, mefenamic acid, and tolfenamic acid, from an aqueous sample. The extraction conditions were optimized with respect to several experimental parameters (dispersive solvent, extraction solvent, pH, salt additive, and concentration) for the simultaneous extraction and analysis of NSAIDs by the response surface methodology based on the central composite design method. The limit of detection and limit of quantitation of the spiked sample were in the concentration range of 0.65–1.3 and 2.2–4.4 µg/L, respectively. The accuracy and precision in the working range were 85–106% and 0.5–10.4% (relative standard deviation), respectively. The linear equations for quantitative analysis were in the concentration range of 0.5–5.0 µg/L with correlation coefficients (R
2 = 0.9990–0.9996).
Down syndrome—A narrative review with a focus on anatomical features
Authors: Arumugam Ashokan , Raja Kavitha , Venugopalan Mahalakshmi , Chandrasekaran Baskaran , Kovanur Sampath Kesava , Muthusamy Hariraja , Shanmugam Nagarani
Published: November 2015

Down syndrome (DS) is the most common aneuploidy of chromosome 21, characterized by the presence of an extra copy of that chromosome (trisomy 21). Children with DS present with an abnormal phenotype, which is attributed to a loss of genetic balance or an excess dose of chromosome 21 genes. In recent years, advances in prenatal screening and diagnostic tests have aided in the early diagnosis and appropriate management of fetuses with DS. A myriad of clinical symptoms resulting from cognitive, physical, and physiological impairments caused by aberrations in various systems of the body occur in DS. However, despite these impairments, which range from trivial to fatal manifestations, the survival rate of individuals with DS has increased dramatically from less than 50% during the mid‐1990s to 95% in the early 2000s, with a median life expectancy of 60 years reported recently. The aim of this narrative review is to review and summarize the etiopathology, prenatal screening and diagnostic tests, prognosis, clinical manifestations in various body systems, and comorbidities associated with DS. Clin. Anat. 29:568–577, 2016. © 2015 Wiley Periodicals, Inc.
Migrated Hopene Synthases from Colysis pothifolia and Identification of a Migration Switch Controlling the Number of 1,2‐Hydride and Methyl Shifts
Authors: Shinozaki Junichi , Hiruta Masayoshi , Okada Takayuki , Masuda Kazuo
Published: November 2015

Ferns are known to produce triterpenes, derived from squalene, that are synthesized by squalene cyclases (SCs). Among these, Colysis species produce onoceroids, the bis‐cyclic skeleton of which can be cyclized from both termini of squalene. To gain insight into the molecular basis of triterpene structural diversity, cDNA cloning of SCs from C. elliptica and C. pothifolia was performed; this leads to the isolation of five SC cDNAs. Functional analysis of these clones revealed their enzymatic products to be hop‐22(29)‐ene, α‐polypodatetraene, and hop‐17(21)‐ene. One of these clones (CPF) is a transcribed pseudogene with a 22‐nucleotide deletion causing a nonsense mutation. To predict the inherent function of CPF, we constructed an insertion mutant of CPF that successfully converted inert CPF to the active SC, the product of which is fern‐9(11)‐ene. Subsequent mutations identified active‐site residues that control the number of 1,2‐hydride and methyl shifts.
Large‐scale mitochondrial DNA deletion underlying familial multiple system atrophy of the cerebellar subtype
Authors: Alsemari Abdulaziz , Al‐hindi Hindi Nasser
Published: November 2015

Key Clinical Message

A family with mitochondrial inheritance of multiple system atrophy of the cerebellar subtype. MRI brain shows significant cerebellar atrophy with mild pontine atrophy and the classical hot cross bun sign in Pons. The muscle biopsy was indicative of mitochondrial myopathy. Mitochondrial DNA analysis revealed a low‐level large mtDNA deletion, m.3264_1607del12806 bp.
Progression of a hepatosplenic gamma delta T‐cell leukemia/lymphoma on hyperCVAD/MTX and ara‐C: literature review and our institutional treatment approach
Authors: Saste Abhijit , Arias‐Stella Javier , Kuriakose Philip
Published: November 2015

Key Clinical Message

A 24‐year‐old male presented with abdominal pain, fever, and palpable splenomegaly. His differential count revealed myelocytes, metamyelocytes, and nucleated red cells. A bone marrow biopsy confirmed a diagnosis of hepatosplenic gamma delta T‐cell leukemia/lymphoma. We describe here our center's diagnostic and treatment approach for this rare leukemia.
The curled sebaceous horn
Authors: Ramdass Michael J.
Published: November 2015

Key Clinical Message

The mysterious sebaceous horn (devil's horn) is a historically perplexing phenomenon of unknown etiology. It classically occurs on the sun‐exposed areas of the face and hands and consists of a keratin mound with a benign base in most cases and squamous cell carcinoma occurring in about 20% of patients.
Poncet's disease mimicking rheumatoid arthritis in a patient with suspected Crohn's disease
Authors: Ariza‐Prota Miguel , Pando‐Sandoval Ana , García‐Clemente Marta , Casan Pere
Published: November 2015

Key Clinical Message

Poncet's disease is a rarely reported entity with an unknown pathogenesis. However, because it has a very favorable prognosis with antituberculosis drugs, we believe it should be considered as a differential diagnosis for patients with fever and polyarthritis of unknown cause, particularly if active tuberculosis is suspected.
Performance of the Solid Oxide Fuel Cell (SOFC)/Proton‐Exchange Membrane Fuel Cell (PEMFC) Hybrid System
Authors: Tan Ling Jun , Yang Chen , Zhou Nana
Published: November 2015

An innovative hybrid power generation system involving a structure‐solid oxide fuel cell (SOFC) and a proton‐exchange membrane fuel cell (PEMFC) is established. A high‐temperature SOFC is not only used to produce electricity, but also supplies the reformed gas to a PEMFC to generate extra electricity simultaneously. A steady‐state thermodynamic model of the SOFC‐PEMFC hybrid system is verified based on the mass and energy balance and the electrochemistry theory. A parametric study is carried out to analyze the effects of various parameters on the performance of the hybrid system. The SOFC operating temperature and the steam‐to‐carbon ratio have a positive impact on the power output and overall efficiency of the system. The operating pressure benefits the system power output but not the overall efficiency. An optimum SOFC fuel utilization factor exists at the highest value of the power output and overall efficiency of the hybrid system.
Catalytic Activity of Cationic and Neutral Silver(I)–XPhos Complexes with Nitrogen Ligands or Tolylsulfonate for Mannich and Aza‐Diels–Alder Coupling Reactions
Authors: Grirrane Abdessamad , Álvarez Eleuterio , García Hermenegildo , Corma Avelino
Published: November 2015

Cationic and neutral silver(I)–L complexes (L=Buchwald‐type biaryl phosphanes) with nitrogen co‐ligands or organosulfonate counter ions have been synthesised and characterised through their structural and spectroscopic properties. At room temperature, both cationic and neutral silver(I)–L complexes are extremely active catalysts in the promotion of the single and double A3 coupling of terminal (di)alkynes, pyrrolidine and formaldehyde. In addition, the aza‐Diels–Alder two‐ and three‐component coupling reactions of Danishefsky’s diene with an imine or amine and aldehyde are efficiently catalysed by these cationic or neutral silver(I)–L complexes. The solvent influences the catalytic performance due to limited complex solubility or solvent decomposition and reactivity. The isolation of new silver(I)–L complexes with reagents as ligands lends support to mechanistic proposals for such catalytic processes. The activity, stability and metal–distal arene interaction of these silver(I)–L catalysts have been compared with those of analogous cationic gold(I) and copper(I) complexes.
Stereoselective Synthesis of 1,3‐Diaminotruxillic Acid Derivatives: An Advantageous Combination of CH‐ortho‐Palladation and On‐Flow [2+2]‐Photocycloaddition in Microreactors
Authors: Serrano Elena , Juan Alberto , García‐Montero Angel , Soler Tatiana , Jiménez‐Márquez Francisco , Cativiela Carlos , Gomez M. Victoria , Urriolabeitia Esteban P.
Published: November 2015

The stereoselective synthesis of ε‐isomers of dimethyl esters of 1,3‐diaminotruxillic acid in three steps is reported. The first step is the ortho‐palladation of (Z)‐2‐aryl‐4‐aryliden‐5(4H)‐oxazolones 1 to give dinuclear complexes 2 with bridging carboxylates. The reaction occurs through regioselective activation of the ortho‐CH bond of the 4‐arylidene ring in carboxylic acids. The second step is the [2+2]‐photocycloaddition of the CC exocyclic bonds of the oxazolone skeleton in 2 to afford the corresponding dinuclear ortho‐palladated cyclobutanes 3. This key step was performed very efficiently by using LED light sources with different wavelengths (465, 525 or 625 nm) in flow microreactors. The final step involved the depalladation of 3 by hydrogenation in methanol to afford the ε‐1,3‐diaminotruxillic acid derivatives as single isomers.
Rapid Non‐Crosslinking Aggregation of DNA‐Functionalized Gold Nanorods and Nanotriangles for Colorimetric Single‐Nucleotide Discrimination
Authors: Wang Guoqing , Akiyama Yoshitsugu , Takarada Tohru , Maeda Mizuo
Published: November 2015

Gold nanoparticles modified with DNA duplexes are rapidly and spontaneously aggregated at high ionic strength. In contrast, this aggregation is greatly suppressed when the DNA duplex has a single‐base mismatch or a single‐nucleotide overhang located at the outermost surface of the particle. These colloidal features emerge irrespective of the size and composition of the particle core; however, the effects of the shape remain unexplored. Using gold nanorods and nanotriangles (nanoplatelets), we show herein that both remarkable rapidity in colloidal aggregation and extreme susceptibility to DNA structural perturbations are preserved, regardless of the shape and aspect ratio of the core. It is also demonstrated that the DNA‐modified gold nanorods and nanotriangles are applicable to naked‐eye detection of a single‐base difference in a gene model. The current study corroborates the generality of the unique colloidal properties of DNA‐functionalized nanoparticles, and thus enhances the feasibility of their practical use.
Characterization of magnetic nanoparticles from Magnetospirillum Gryphiswaldense as potential theranostics tools
Authors: Orlando T. , Mannucci S. , Fantechi E. , Conti G. , Tambalo S. , Busato A. , Innocenti C. , Ghin L. , Bassi R. , Arosio P. , Orsini F. , Sangregorio C. , Corti M. , Casula M. F. , Marzola P. , Lascialfari A. , Sbarbati A.
Published: November 2015

We investigated the theranostic properties of magnetosomes (MNs) extracted from magnetotactic bacteria, promising for nanomedicine applications. Besides a physico‐chemical characterization, their potentiality as mediators for magnetic fluid hyperthermia and contrast agents for magnetic resonance imaging, both in vitro and in vivo, are here singled out. The MNs, constituted by magnetite nanocrystals arranged in chains, show a superparamagnetic behaviour and a clear evidence of Verwey transition, as signature of magnetite presence. The phospholipid membrane provides a good protection against oxidation and the MNs oxidation state is stable over months. Using an alternate magnetic field, the specific absorption rate was measured, resulting among the highest reported in literature. The MRI contrast efficiency was evaluated by means of the acquisition of complete NMRD profiles. The transverse relaxivity resulted as high as the one of a former commercial contrast agent. The MNs were inoculated into an animal model of tumour and their presence was detected by magnetic resonance images two weeks after the injection in the tumour mass. Copyright © 2015 John Wiley & Sons, Ltd.
Nonoperative management of rectal cancer
Authors: Torok Jordan A. , Palta Manisha , Willett Christopher G. , Czito Brian G.
Published: November 2015

Surgery has long been the primary curative modality for localized rectal cancer. Neoadjuvant chemoradiation has significantly improved local control rates and, in a significant minority, eradicated all disease. Patients who achieve a pathologic complete response to neoadjuvant therapy have an excellent prognosis, although the combination treatment is associated with long‐term morbidity. Because of this, a nonoperative management (NOM) strategy has been pursued to preserve sphincter function in select patients. Clinical and radiographic findings are used to identify patients achieving a clinical complete response to chemoradiation, and they are then followed with intensive surveillance. Incomplete, nonresponding and those demonstrating local progression are referred for salvage with standard surgery. Habr‐Gama and colleagues have published extensively on this treatment strategy and have laid the groundwork for this approach. This watch‐and‐wait strategy has evolved over time, and several groups have now reported their results, including recent prospective experiences. Although initial results appear promising, several significant challenges remain for NOM of rectal cancer. Further study is warranted before routine implementation in the clinic. Cancer 2016;122:34–41. © 2015 American Cancer Society.
Kinetic block model of crystal–mother‐phase interface with preferential clustering ‐ single layer case
Authors: Izdebski Marek , Włodarska Magdalena
Published: November 2015

A new single‐layer kinetic block model of crystal growth is proposed, which takes into account preference for bonds between blocks of the same type over mixed‐type bonds. The obtained parameters describing stable growth conditions were compared with other theoretical models (such as thermodynamic Jackson model and the earlier proposed kinetic model based on zeroth order approximation) which assume that new growth units are attached in a completely random way. Additionally, the results were compared with Monte Carlo simulations. The proposed model produced results which matched the simulation results much better than the other theoretical models. The new model can be used for studying crystal growth both from solution and from vapour. Calculations based on this model show that the number of created mixed‐type bonds depends on the temperature and is lower from its estimation obtained with the use of the zeroth order (Bragg‐Williams) approximation.
Conversion of Biomass Derivatives to Electricity in Photo Fuel Cells using Undoped and Tungsten‐doped Bismuth Vanadate Photoanodes
Authors: Zhang Bingqing , Shi Jingying , Ding Chunmei , Chong Ruifeng , Zhang Bao , Wang Zhiliang , Li Ailong , Liang Zhenxing , Liao Shijun , Li Can
Published: November 2015

The photo fuel cell (PFC) is a promising technology for simultaneously converting solar energy and bioenergy into electricity. Here, we present a miniature air‐breathing PFC that uses either BiVO4 or W‐doped BiVO4 as the photoanode and a Pt/C catalyst as the air‐breathing cathode. The PFC exhibited excellent performance under solar illumination and when fed with several types of biomaterial. We found the PFC performance could be significantly enhanced using W‐doping into the BiVO4 photoanode. With glucose as the fuel and simulated sunlight (AM 1.5 G) as the light source, the open‐circuit voltage increased from 0.74 to 0.92 V, the short‐circuit current density rose from 0.46 to 1.62 mA cm−2, and the maximum power density was boosted from 0.05 to 0.38 mW cm−2, compared to a PFC using undoped BiVO4 as the anode.
Combining the least cost path method with population genetic data and species distribution models to identify landscape connectivity during the late Quaternary in Himalayan hemlock
Authors: Yu Haibin , Zhang Yili , Liu Linshan , Qi Wei , Li Shicheng , Hu Zhongjun
Published: November 2015

Himalayan hemlock (Tsuga dumosa) experienced a recolonization event during the Quaternary period; however, the specific dispersal routes are remain unknown. Recently, the least cost path (LCP) calculation coupled with population genetic data and species distribution models has been applied to reveal the landscape connectivity. In this study, we utilized the categorical LCP method, combining species distribution of three periods (the last interglacial, the last glacial maximum, and the current period) and locality with shared chloroplast, mitochondrial, and nuclear haplotypes, to identify the possible dispersal routes of T. dumosa in the late Quaternary. Then, both a coalescent estimate of migration rates among regional groups and establishment of genetic divergence pattern were conducted. After those analyses, we found that the species generally migrated along the southern slope of Himalaya across time periods and genomic makers, and higher degree of dispersal was in the present and mtDNA haplotype. Furthermore, the direction of range shifts and strong level of gene flow also imply the existence of Himalayan dispersal path, and low area of genetic divergence pattern suggests that there are not any obvious barriers against the dispersal pathway. Above all, we inferred that a dispersal route along the Himalaya Mountains could exist, which is an important supplement for the evolutionary history of T. dumosa. Finally, we believed that this integrative genetic and geospatial method would bring new implications for the evolutionary process and conservation priority of species in the Tibetan Plateau.
Matrix quality and disturbance frequency drive evolution of species behavior at habitat boundaries
Authors: Martin Amanda E. , Fahrig Lenore
Published: November 2015

Previous theoretical studies suggest that a species' landscape should influence the evolution of its dispersal characteristics, because landscape structure affects the costs and benefits of dispersal. However, these studies have not considered the evolution of boundary crossing, that is, the tendency of animals to cross from habitat to nonhabitat (“matrix”). It is important to understand this dispersal behavior, because of its effects on the probability of population persistence. Boundary‐crossing behavior drives the rate of interaction with matrix, and thus, it influences the rate of movement among populations and the risk of dispersal mortality. We used an individual‐based, spatially explicit model to simulate the evolution of boundary crossing in response to landscape structure. Our simulations predict higher evolved probabilities of boundary crossing in landscapes with more habitat, less fragmented habitat, higher‐quality matrix, and more frequent disturbances (i.e., fewer generations between local population extinction events). Unexpectedly, our simulations also suggest that matrix quality and disturbance frequency have much stronger effects on the evolution of boundary crossing than either habitat amount or habitat fragmentation. Our results suggest that boundary‐crossing responses are most affected by the costs of dispersal through matrix and the benefits of escaping local extinction events. Evolution of optimal behavior at habitat boundaries in response to the landscape may have implications for species in human‐altered landscapes, because this behavior may become suboptimal if the landscape changes faster than the species' evolutionary response to that change. Understanding how matrix quality and habitat disturbance drive evolution of behavior at boundaries, and how this in turn influences the extinction risk of species in human‐altered landscapes should help us identify species of conservation concern and target them for management.
Modeling behavioral thermoregulation in a climate change sentinel
Authors: Moyer‐Horner Lucas , Mathewson Paul D. , Jones Gavin M. , Kearney Michael R. , Porter Warren P.
Published: November 2015

When possible, many species will shift in elevation or latitude in response to rising temperatures. However, before such shifts occur, individuals will first tolerate environmental change and then modify their behavior to maintain heat balance. Behavioral thermoregulation allows animals a range of climatic tolerances and makes predicting geographic responses under future warming scenarios challenging. Because behavioral modification may reduce an individual's fecundity by, for example, limiting foraging time and thus caloric intake, we must consider the range of behavioral options available for thermoregulation to accurately predict climate change impacts on individual species. To date, few studies have identified mechanistic links between an organism's daily activities and the need to thermoregulate. We used a biophysical model, Niche Mapper, to mechanistically model microclimate conditions and thermoregulatory behavior for a temperature‐sensitive mammal, the American pika (Ochotona princeps). Niche Mapper accurately simulated microclimate conditions, as well as empirical metabolic chamber data for a range of fur properties, animal sizes, and environmental parameters. Niche Mapper predicted pikas would be behaviorally constrained because of the need to thermoregulate during the hottest times of the day. We also showed that pikas at low elevations could receive energetic benefits by being smaller in size and maintaining summer pelage during longer stretches of the active season under a future warming scenario. We observed pika behavior for 288 h in Glacier National Park, Montana, and thermally characterized their rocky, montane environment. We found that pikas were most active when temperatures were cooler, and at sites characterized by high elevations and north‐facing slopes. Pikas became significantly less active across a suite of behaviors in the field when temperatures surpassed 20°C, which supported a metabolic threshold predicted by Niche Mapper. In general, mechanistic predictions and empirical observations were congruent. This research is unique in providing both an empirical and mechanistic description of the effects of temperature on a mammalian sentinel of climate change, the American pika. Our results suggest that previously underinvestigated characteristics, specifically fur properties and body size, may play critical roles in pika populations' response to climate change. We also demonstrate the potential importance of considering behavioral thermoregulation and microclimate variability when predicting animal responses to climate change.
Synthesis of Deuterium‐Labelled 3‐Hydroxy‐L‐arginine: Comparative Studies on Different Protecting‐Group Strategies
Authors: Lemke Anke , Ducho Christian
Published: November 2015

The β‐hydroxy‐α‐amino acid 3‐hydroxy‐L‐arginine is an important intermediate in biosynthetic pathways involving 2‐oxoglutarate (2‐OG) dependent FeII oxygenases. It also plays an essential role in post‐translational modifications of ribosomal proteins. For profound studies on arginine‐hydroxylating enzymes, synthetic reference compounds are of utmost importance. However, the synthesis of β‐hydroxy‐α‐amino acids is often not trivial. In particular, the preparation of a densely functionalized compound such as 3‐hydroxy‐L‐arginine poses a challenge in terms of a protecting‐group strategy. We have previously established a concise synthesis of 3‐hydroxy‐L‐arginine that is suitable for the preparation of both 3‐epimers of this β‐hydroxy‐α‐amino acid. However, we have since observed a remarkable isomerization reaction upon removal of the hydrogenolytically cleavable protecting groups, thus limiting the reliability of our previously described route. In this paper, we report a comparative study of protecting‐group strategies for this synthetic route, including a newly developed, more robust pathway to the target amino acid. The versatility of this improved route is demonstrated by the synthesis of the deuterium‐labelled derivatives (3R)‐ and (3S)‐3‐hydroxy‐[5‐2H]‐L‐arginine. These new isotope‐labelled arginine derivatives represent important tools for the elucidation of biosynthetic pathways, such as the formation of the arginine‐derived amino acid epicapreomycidine in the biosynthesis of muraymycin nucleoside antibiotics.
Regioselective Coupling Reactions of Coumarins with Aldehydes or Di‐tert‐butyl Peroxide (DTBP) through a C(sp2)–H Functionalization Process
Authors: Zhao Wannian , Xu Lei , Ding Yingcai , Niu Ben , Xie Ping , Bian Zhaogang , Zhang Denghong , Zhou Aihua
Published: November 2015

Coumarin derivatives are highly valuable compounds in drug discovery. Herein, we have developed two new coupling reactions that involve coumarins and either aldehydes or di‐tert‐butyl peroxide (DTBP) in the presence of inexpensive copper or iron catalysts. Both of these reactions proceed through a C(sp2)–H functionalization process to regioselectivity generate keto‐ or methyl‐substituted coumarin derivatives in moderate to good yields These coupling reactions will enrich current coumarin chemistry.
A Chiral Building Block for the ­Stereocontrolled Installation of the 1,3‐Diol Motif
Authors: Bredenkamp Angela , Zhu Zhi‐Bin , Kirsch Stefan F.
Published: November 2015

A new chiral building block for the direct installation of the 1,3‐diol motif is presented. Aldehyde olefination followed by directed reduction allows for the synthesis of both the syn‐ and the anti‐configured diol in a fully stereocontrolled way. The building block was used for the total synthesis of naturally occurring 1,2,4‐trihydroxynonadecanes starting from pentadecanal.
Tandem C–C Bond Cleavage of ­Cyclopropanols and Oxidative Aromatization by Manganese(IV) Oxide in a Direct C–H to C–C Functionalization of Heteroaromatics
Authors: Bume Desta Doro , Pitts Cody Ross , Lectka Thomas
Published: November 2015

We report a direct C–H to C–C bond functionalization of electron‐deficient heteroaromatics enabled by mild C–C bond cleavage of cyclopropanols as a new route to β‐aryl carbonyl‐containing products. Additionally, as an alternative to using a “catalyst” that requires an excess amount of a sacrificial oxidant for regeneration and/or oxidative aromatization, this paper features manganese(IV) oxide as an inexpensive “dual role” reagent – effecting both C–C bond cleavage and ultimate rearomatization. Under the specified conditions, a variety of heterocycles proved competent for regioselective C–C bond formation, alongside a diverse array of cyclopropanols with broad functional‐group tolerance. We highlight applications to complex‐molecule synthesis and direct derivatization of biologically active alkaloids. Furthermore, kinetic isotope effect (KIE) experiments, radical scavengers, and some insight into the application of tri‐ and tetravalent manganese species are invoked to shape an initial mechanistic hypothesis.
A Paper‐based Mitochondrial Electrochemical Biosensor for Pesticide Detection
Authors: Wang Tao , Reid Russell C. , Minteer Shelley D.
Published: November 2015

In this article, we detail a paper‐based three‐electrode electrochemical biosensor using a mitochondria modified Toray carbon paper working electrode. Cyclic voltammetry performed on the paper‐based biosensor and similar electrodes in a common laboratory setup (not in an integrated paper‐based device) compare favorably. In addition, instant detection of malathion with a detection limit of 20 nM by cyclic voltammetry is demonstrated, showing the device can potentially be used as a portable platform for pesticides detection.
Construction of 5‐amino‐1,10‐phenanthroline‐Fe(II) Nanostructures on Glassy Carbon Electrode: Simultaneous and Selective Determination of Purine and Pyrimidine DNA Bases
Authors: Shervedani Reza Karimi , Dehaghi Sedigheh Bagheri , Foroushani Marzieh Samiei
Published: November 2015

5‐amino‐1,10‐phenanthroline‐Fe(II) complex is immobilized onto GC electrode and used for determination of DNA bases. Modifications are traced by electrochemical methods. All DNA bases are electroactive on the modified electrode. The Ips increased linearly with increase of DNA bases concentration. A wide response range was observed for each base (∼4 orders for guanine (GA) and adenine (A); and ∼2.5 orders for thymine (T) and cytosine (C)) with DLs of 0.15, 4.44, 133.0 and 230.0 nM, respectively. The electrode was applied for determination of calf‐thymus DNA bases. The value obtained for [(GA+C)/(A+T)], 0.78, is in good agreement with standard value, 0.77.
New Potentiometric Sensor for the Determination of Bromate Ion in Drinking Water
Authors: Saber Amr L.
Published: November 2015

The characteristics, performance and application of ion‐selective electrodes for bromate ion based on rhodamine B and tetrahexyl ammonium bromide as electrode‐active substances are described for the first time. These electrodes respond with sensitivities of (58.0±1.0) and (61.0±2.0) mV decade−1over the range 1.0×10−8–1.0×10−2 mol l−1at pH 4–9 and 4–8 and a detection limit of 6.0×10−8and 4.0×10−8 mol l−1for rhodamine B and tetrahexyl ammonium bromide sensors, respectively. The electrodes are easily constructed at a relatively low cost, have a fast response time and can be used for a period of 3 months without any considerable divergence in potential. The proposed sensors displayed good selectivity for bromate ion in the presence of several substances and inorganic anions. Sensors were used for the direct assay of bromate ion in drinking water samples.
Enzyme Based Electrochemical Biosensor for Ethanolamine
Authors: Sikarwar Bhavna , Sharma Pushpendra K. , Tripathi Brajesh K. , Boopathi Mannan , Singh Beer , Jaiswal Yogesh K.
Published: November 2015

Enzyme based electrochemical detection method developed for chemical toxicant ethanolamine (EA). Monoamine oxidase A (MAO‐A) enzyme was used for the oxidation of EA. A direct electron transfer from the electrode to EA without any mediator with the help of MAO‐A enzyme was attained and this confirms the application of this methodology for the development of third generation biosensor for EA sensing well below the IDLH (30 ppm) value of EA. Moreover, heterogeneous rate constant (0.021s−1) and the number of electron involved (5.2) were deduced for EA in PBS buffer. The calibration plot showed linearity 2.02×10−4 M to 10.10×10−4 M of EA in PBS buffer with detection limit 4.1 ppm. The modified electrodes are characterized by Raman and Electrochemical impedance spectroscopy (EIS) techniques. The outcome of this work indicates about the utility of this methodology for the sensing of EA in the environment if it is present as well as to degrade EA into other compounds without using any indicator or mediator.
Mathematical modeling of cell growth in a 3D scaffold and validation of static and dynamic cultures
Authors: Mokhtari‐Jafari Fatemeh , Amoabediny Ghassem , Haghighipour Nooshin , Zarghami Reza , Saatchi Alireza , Akbari Javad , Salehi‐Nik Nasim
Published: November 2015

Tissue engineering, an immensely important field in contemporary clinical practices, aims at the repair or replacement of damaged tissues. The mathematical model proposed herein shows the distribution and growth of cells in their characteristic time in a 3D scaffold model. This study contributes to the progress of simulation techniques in static and dynamic cultures of bone tissue. Brinkman, nutrient transport, and cell growth equations are brought together to quantify the growth behavior of cells. However, when a static culture is being studied, the Brinkman equation is eliminated. The model was validated by experimental cell culture using 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay and scanning electron microscopy. Then, static and dynamic cultures were compared to assess the cell density and cell distribution in the scaffold. Cell counting after 21 days of cell culture showed that the number of cells increased 42‐fold in static and 53.5‐fold in dynamic cultures, which was in good agreement with our model estimations (37‐fold increase in the number of cells in static and 49‐fold increase in dynamic cultures). In conclusion, our mathematical model could predict cell distribution and growth in the scaffold.
Effectiveness of impregnation of ammonium polyphosphate fire retardant in poplar wood using microwave heating
Authors: He Xia , Li Xian Jun , Zhong Zhu , Mou Qunying , Yan Yonglin , Chen Hongbin , Liu Linghong
Published: November 2015

Poplar samples were impregnated with ammonium polyphosphate fire retardant at various pressures and durations after they were pretreated with microwave heating. The effects of the pressure and duration on the flame‐retardation and smoke‐suppression properties were investigated with cone calorimeter analysis. The peak heat release rate (pk‐HRR), total heat release (THR), and total smoke product (TSP) of treated woods were measured for samples of pretreated and untreated with microwave. After the impregnation, the poplar wood showed the significant improvement in its fire resistance. Compared with non‐impregnation wood, the pk‐HRR, THR, and TSP of wood impregnated with ammonium polyphosphate at pressure of 0.4 MPa and duration of 10 min were 48.29%, 35.58%, and 68.64% less, respectively. The pk‐HRR, THR, and TSP of microwave pretreated wood was 15.89%, 5.69%, and 13.59% less than those without microwave pretreated sample. The microwave pretreatment of wood can increase fire retardant effectiveness of ammonium polyphosphate‐impregnated wood. Copyright © 2015 John Wiley & Sons, Ltd.