bluuebunny/crossref_metadata_2025 huggingface dataset:
Spatial abilities and anatomy knowledge assessment: A systematic review
Authors: Langlois Jean , Bellemare Christian , Toulouse Josée , Wells George A.
Published: October 2016

Anatomy knowledge has been found to include both spatial and non‐spatial components. However, no systematic evaluation of studies relating spatial abilities and anatomy knowledge has been undertaken. The objective of this study was to conduct a systematic review of the relationship between spatial abilities test and anatomy knowledge assessment. A literature search was done up to March 20, 2014 in Scopus and in several databases on the OvidSP and EBSCOhost platforms. Of the 556 citations obtained, 38 articles were identified and fully reviewed yielding 21 eligible articles and their quality were formally assessed. Non‐significant relationships were found between spatial abilities test and anatomy knowledge assessment using essays and non‐spatial multiple‐choice questions. Significant relationships were observed between spatial abilities test and anatomy knowledge assessment using practical examination, three‐dimensional synthesis from two‐dimensional views, drawing of views, and cross‐sections. Relationships between spatial abilities test and anatomy knowledge assessment using spatial multiple‐choice questions were unclear. The results of this systematic review provide evidence for spatial and non‐spatial methods of anatomy knowledge assessment. Anat Sci Educ 10: 235–241. © 2016 American Association of Anatomists.
meso‐N‐Pyrrole as a Versatile Substituent Influencing the Optical Properties of Porphyrin
Authors: Hurej Karolina , Stawski Wojciech , Latos‐Grażyński Lechosław , Pawlicki Miłosz
Published: October 2016

A meso‐N‐pyrrole porphyrin converts into a π‐extended porphyrin forming an indolizine‐3‐one motif. The indolizine‐3‐one frame opens a lactam subunit preserving a six‐membered, heterocyclic structure fused with the main macrocycle. The optical properties of formed derivatives follow the structural modifications giving the absorbance and emission eventually modulated by the NH‐centered modifications of the fused unit.
Fault‐Tolerant Finite Frequency H∞ Control for Uncertain Mechanical System with Input Delay and Constraint
Authors: Xu Shidong , Sun Guanghui , Sun Weichao
Published: October 2016

In this paper, a novel fault‐tolerant finite frequency H∞ controller (FFHC) is developed for uncertain mechanical system with input delay and constraint. First, the mathematical model of uncertain mechanical system is derived, where the uncertainties occur in mass, damping and stiffness matrices, respectively. Then, in view of the fact that the dominant resonance energies are caused by low‐order vibration modes of mechanical system, the finite frequency control algorithm is investigated to suppress these low‐order resonances peaks. By virtue of Lyapunov‐Krasovskii functional (LKF) and generalized Kalman‐Yakubovich‐Popov (GKYP) lemma, the desirable fault‐tolerant controller can be obtained by convex optimization. Numerical simulations verify the improvements and advantages of proposed cotroller in disturbance rejection when compared with the classic entire frequency H∞ controller (EFHC).
Impacts of initial structure of tropical cyclone on secondary eyewall formation
Authors: Ge Xuyang , Guan Liang , Zhou Shunwu
Published: October 2016

The secondary eyewall replacement cycle (ERC) is an important aspect for tropical cyclone (TC) intensity and structure forecasts. Both observational studies and idealized simulations are conducted to explore the sensitivity of secondary eyewall formation (SEF) to the initial structure of the tropical cyclone. It is found that a TC with a larger size (i.e. both the radial of maximum wind and outer size) is apt to SEF. Furthermore, a larger TC likely has a potential to form a larger outer eyewall and thus a wider moat region. The different SE structures may lead to different intensity fluctuations. This study motivates further research with respect to how initial structure influences the storm intensity and structure changes.
The relationship between summer sea ice extent in Hudson Bay and the Arctic Ocean via the atmospheric circulation
Authors: Ogi Masayo , Barber David G. , Rysgaard Søren
Published: October 2016

The trends and interannual variations of summer sea ice extents (SIEs) in both Hudson Bay and the Arctic Ocean are investigated in association with variations in atmospheric circulation and air temperature. The summer SIE variabilities of both Hudson Bay and the Arctic Ocean are well correlated and have a strong negative trend. The negative SIE trends are associated with a summer atmospheric circulation pattern that is characterized by positive anomalies over the Arctic Ocean and negative anomalies over mid‐latitudes. The trends are also connected with warm air temperatures over mid‐ and high‐latitudes. The atmospheric circulation and air temperature regressed on the summer SIEs in both Hudson Bay and the Arctic Ocean are quite similar to these trend patterns. On the other hand, the year‐to‐year variations of the detrended summer SIEs in both Hudson Bay and the Arctic Ocean are not correlated. The summer atmospheric circulation and air temperature over the Arctic Ocean have contributed to the detrended summer Arctic Ocean SIE. In contrast, the detrended summer Hudson Bay SIE is controlled by atmospheric circulation and air temperature in the previous spring.
Discovery of Novel Striatal‐enriched Protein Tyrosine Phosphatase Inhibitors Through Structure‐based Virtual Screening
Authors: Ku Bonsu , You Jin A , Lee Hye Seon , Shin Ho‐Chul , Park Hwangseo , Kim Seung Jun
Published: October 2016

Striatal‐enriched protein tyrosine phosphatase (STEP) is considered a potential target for the development of therapeutics for neurodegenerative diseases and cocaine addiction. We herein report 10 novel STEP inhibitors identified using a combination of in silico structure‐based virtual screening with an accurate solvation free energy term‐applied improved scoring function and in vitro phosphatase inhibition assay. These compounds, computationally selected for their advantageous physicochemical properties as drug candidates, exhibited micromolar IC50
values of 3.21–10.6 μM. Enzyme kinetic assays together with structure‐based docking simulations suggested that three most potent inhibitors are novel surrogates for phosphotyrosine that are accommodated at the active site of STEP. We expect that identification of these compounds will provide a foundation for further improvement and optimization to develop STEP‐targeting drug candidate molecules.
Development of the Anatomical Quality Assessment (AQUA) Tool for the quality assessment of anatomical studies included in meta‐analyses and systematic reviews
Authors: Henry Brandon Michael , Tomaszewski Krzysztof A. , Ramakrishnan Piravin Kumar , Roy Joyeeta , Vikse Jens , Loukas Marios , Tubbs R. Shane , Walocha Jerzy A.
Published: October 2016

Critical appraisal of anatomical studies is essential before the evidence from them undergoes meta‐epidemiological synthesis. However, no instrument for appraising anatomical studies with inherent applicability to different study designs is available. We aim to develop a generic yet comprehensive tool for assessing the quality of anatomical studies using a formal consensus method. The study steering committee formulated an initial conceptual design and generated items for a preliminary tool on the basis of a literature review and expert opinion. A Delphi procedure was then adopted to assess the validity of the preliminary tool. Feedback from the Delphi panelists was used to improve it. The Delphi procedure involved 12 experts in anatomical research. It comprised two rounds, after which unanimous consensus was reached about the items to be included. The preliminary tool consisted of 20 items, which were phrased as signaling questions and organized into five domains: 1. Aim and subject characteristics, 2. Study design, 3. Characterization of methods, 4. Descriptive anatomy, and 5. Results reporting. Each domain was set to end with a risk of bias question. Following round 1, some of the items underwent major revision, although agreement was reached regarding inclusion of all the domains and signaling questions in the preliminary tool. The tool was revised only for minor language inaccuracies after round 2. The AQUA Tool was designed to assess the quality and reliability of anatomical studies. It is currently undergoing a validation process. Clin. Anat. 30:6–13, 2017. © 2016 Wiley Periodicals, Inc.
Direct effect of dasatinib on signal transduction pathways associated with a rapid mobilization of cytotoxic lymphocytes
Authors: Iriyama Noriyoshi , Hatta Yoshihiro , Takei Masami
Published: October 2016

It has been shown that an increase in cytotoxic lymphocyte counts in the peripheral blood occurs rapidly after taking dasatinib, but the underlying mechanism is not yet elucidated. To investigate the influence of dasatinib on signal transduction pathways, we investigated the changes in JAK‐STAT, mitogen‐activated protein kinase (MAPK), and AKT in cytotoxic lymphocytes, including natural killer (NK) cells and cytotoxic T lymphocytes (CTLs), before and after dasatinib treatment in chronic myeloid leukemia patients. Among a total of 30 patients, 18 were treated with dasatinib, nine with imatinib, and three with nilotinib. At constitutive levels, the expression of phosphorylated proteins, pSTAT1, pSTAT3, and pERK in NK cells and pSTAT3 in CTLs, was significantly higher in dasatinib‐treated patients. Among the patients evaluated, only dasatinib‐treated patients showed inhibition of multiple signaling pathways after taking a tyrosine kinase inhibitor. The magnitude of pERK and pAKT inhibition was closely associated with an increase in NK cells and CTLs, respectively, after taking a tyrosine kinase inhibitor. Those responses were more evident in patients with cytomegalovirus IgG positivity. In this study, we demonstrated for the first time, the influence of dasatinib on cell events in cytotoxic lymphocytes in vivo and explained the possible underlying mechanism that results in lymphocyte mobilization after dasatinib treatment.
CXCL9: evidence and contradictions for its role in tumor progression
Authors: Ding Qiang , Lu Panpan , Xia Yujia , Ding Shuping , Fan Yuhui , Li Xin , Han Ping , Liu Jingmei , Tian Dean , Liu Mei
Published: October 2016

Chemokines are a group of low molecular weight peptides. Their major function is the recruitment of leukocytes to inflammation sites, but they also play a key role in tumor growth, angiogenesis, and metastasis. In the last few years, accumulated experimental evidence supports that monokine induced by interferon (IFN)‐gamma (CXCL9), a member of CXC chemokine family and known to attract CXCR3‐ (CXCR3‐A and CXCR3‐B) T lymphocytes, is involved in the pathogenesis of a variety of physiologic diseases during their initiation and their maintenance. This review for the first time presents the most comprehensive summary for the role of CXCL9 in different types of tumors, and demonstrates its contradictory role of CXCL9 in tumor progression. Altogether, this is a useful resource for researchers investigating therapeutic opportunities for cancer.
Follow model for incorporating FARs into your athletics compliance program
Authors: McCarthy Claudine
Published: October 2016

Faculty Athletics Representatives can play valuable roles in your athletics department's compliance program. In fact, FARs should become incorporated into such aspects as certification of eligibility and compliance education, as well as serving in advisory roles and as liaisons between your school and athletics department.
Prevent abusive coaching by monitoring coaches, reinforcing proper behavior
Authors: McCarthy Claudine
Published: October 2016

It can be a tough call to make — identifying the line between demanding versus demeaning coaching. But there's almost no call more critical to the success of your athletics department. When the call is made correctly, and the difference is easily recognized, you'll see a great decrease in the liability and risk levels for your department.
Boost success by encouraging coaches, staff to embrace positive leadership model
Authors: McCarthy Claudine
Published: October 2016

Despite the fact that studies reveal positive leadership brings more success than a negative approach, criticism and other forms of negativity still abound in the college sports environment.
Prevent overload and improve productivity, organization
Authors: McCarthy Claudine
Published: October 2016

If you frequently wonder where the time went, experience information overload, or become sucked into round‐the‐clock emails, then consider taking specific steps to boost your productivity and organization.
Determinants of consumer attitude toward corporate sponsors: A comparison between a profit and nonprofit sport event sponsorship
Authors: Ko Yong Jae , Chang Yonghwan , Park Chanmin , Herbst Frikkie
Published: October 2016

The purposes of the present study were to identify key attributes of sponsors that positively influence consumers' attitude formation and to examine the moderator role of sport event types (nonprofit vs. profit). Based on the theories of range and selective attention, we hypothesized that consumers weigh differently on particular sponsorship attributes depending on event type (i.e., profit vs. nonprofit) in constructing their attitude. The study utilized multi‐group structural equation modeling on data collected by questionnaire survey from a total of 505 spectators of college sport event (n = 303) and FIFA World Cup (n = 202). Results of structural equation modeling test indicate that prominence of sponsors is an important predictor of consumer attitude in both events, while sincerity of sponsors was found to be important in local and amateur college sport event sponsorship. From a theoretical perspective, the current study sheds light on sponsorship study, particularly the importance of examining sponsor characteristics in predicting consumer attitude and the event type as a moderating variable. A key practical implication is that sport managers should carefully examine consumers' perceptions toward sponsor characteristics in making their event sponsorship decisions. Copyright © 2016 John Wiley & Sons, Ltd.
Recombinant human endostatin inhibits TNF‐alpha‐induced receptor activator of NF‐κB ligand expression in fibroblast‐like synoviocytes in mice with adjuvant arthritis
Authors: Gao Qiu‐Fang , Zhang Xiu‐Hong , Yuan Feng‐Lai , Zhao Ming‐Dong , Li Xia
Published: October 2016

Bone loss is a critical pathology responsible for the functional disability in patients with rheumatoid arthritis (RA). It is well known that receptor activator of nuclear factor kappa‐B (NF‐κB) ligand (RANKL) plays a crucial role in bone loss in RA. The purpose of this study was to determine whether recombinant human endostatin (rh‐endostatin) mediates bone erosion in RA by regulation of RANKL expression in an experimental model of RA, consisting of mice with adjuvant‐induced arthritis (AA). Cultured AA fibroblast‐like synoviocytes (FLSs) obtained from these mice were induced by tumor necrosis factor‐α (TNF‐α) combined with or without rh‐endostatin. The levels of RANKL and osteoprotegerin (OPG) mRNA, soluble and membrane‐bound proteins were assessed by real‐time PCR, ELISA, and Western blotting. Western blotting and the luciferase reporter assay were used to study related signaling pathways. Rh‐endostatin inhibited RANKL mRNA expression, soluble and membrane‐bound protein expression in AA FLSs but not in CD4+ T cells. However, OPG expression and secretion was not affected by rh‐endostatin in AA FLSs. Molecular analysis demonstrated that rh‐endostatin significantly inhibited TNF‐α‐induced MAPK and AP‐1 signaling pathways. Moreover, rh‐endostatin attenuated TNF‐α‐induced NF‐κB signaling by suppressing the phosphorylation level of inhibitor kappaBα (IκBα) and nuclear translocation of NF‐κB p65 in FLSs from mice with AA. These results provide the first evidence that rh‐endostatin inhibits TNF‐α‐induced RANKL expression in AA FLSs.
Tamoxifen inhibits mitochondrial oxidative stress damage induced by copper orthophenanthroline
Authors: Buelna‐Chontal Mabel , Hernández‐Esquivel Luz , Correa Francisco , Díaz‐Ruiz Jorge Luis , Chávez Edmundo
Published: October 2016

In this work, we studied the effect of tamoxifen and cyclosporin A on mitochondrial permeability transition caused by addition of the thiol‐oxidizing pair Cu2+‐orthophenanthroline. The findings indicate that tamoxifen and cyclosporin A circumvent the oxidative membrane damage manifested by matrix Ca2+ release, mitochondrial swelling, and transmembrane electrical gradient collapse. Furthermore, it was found that tamoxifen and cyclosporin A prevent the generation of TBARs promoted by Cu2+‐orthophenanthroline, as well as the inactivation of the mitochondrial enzyme aconitase and disruption of mDNA. Electrophoretic analysis was unable to demonstrate a cross‐linking reaction between membrane proteins. Yet, it was found that Cu2+‐orthophenanthroline induced the generation of reactive oxygen species. It is thus plausible that membrane leakiness is due to an oxidative stress injury.
Mature CD8+ T‐cell clonal expansion in the oral cavity and digestive tract: a severe lymphoid malignancy that mimics Crohn's disease
Authors: Coppo Paul , Fabiani Bettina , Marzac Christophe , Sokol Harry
Published: October 2016

Key Clinical Message

In patients with atypical Crohn's disease features, including severe oral ulcerations and resistance to standard treatment, the possibility of a mature clonal CD8+ T‐cell lymphoproliferative disorder should be investigated. Clinicians should be aware of this differential diagnosis because CD8+ T‐cell lymphoma prognosis can be remarkably favorable upon oral treatment with cyclophosphamide.
Kinetic Modeling and Reactor Simulation for Ethanol Steam Reforming
Authors: Tripodi Antonio , Compagnoni Matteo , Rossetti Ilenia
Published: October 2016

An extended kinetic model has been proposed for the ethanol steam reforming reaction that includes kinetic steps for the formation of important byproducts such as ethylene, acetaldehyde, and coke. The model has been applied to the regression of new kinetic data obtained with the use of a 9 wt % K2O/10 wt % Ni/ZrO2 catalyst prepared by flame pyrolysis. The kinetic tests were performed by varying the temperature, space velocity, and the water/ethanol ratio according to a central composite experimental design. The model was validated against literature data collected over a different catalytic system and without the presence of the selected byproducts to check its versatility and robustness. The model gave very straightforward predictions of catalyst performance for the literature data: in this case the lump sum of all the square residues (calculated vs. tabulated mol fractions) is 2.88×10−2 over a dataset of 408 points. For our own kinetic data, the model interpreted the conversion of ethanol and the evolution of the main byproducts, which include ethylene and acetaldehyde, correctly. The evolution of coke was interpreted less satisfactorily because of a missing step for coke gasification. Rate‐limiting steps have been identified together with very rapid reaction steps, which can be considered to be substantially equilibrated.
Novel Functional Hollow and Multihollow Organic Microspheres: Enhanced Efficiency in a Complex, Heterogeneous, Asymmetric, Three‐Component/Triple Organocascade Reaction
Authors: Dai Fuqiang , Zhao Zhiwei , Xie Guangxin , Feng Dandan , Ma Xuebing
Published: October 2016

The pioneered construction of monodisperse hollow and multihollow Jørgensen–Hayashi‐functionalized microspheres with a well‐defined spherical morphology, high surface area, and large pore volume were developed by initial dispersion copolymerization of the Jørgensen–Hayashi organocatalyst with acrylamide and styrene monomers cross‐linked by p‐divinylbenzene and ethylene glycol dimethacrylate, respectively, on the surface of poly(styrene/acrylic acid) (PS) microspheres to form core–shell structures, followed by removal of the PS core by etching in organic solvents. The as‐prepared hollow and multihollow microspheres were able to achieve better mass transfer in a complex heterogeneous asymmetric three‐component/triple cascade reaction and provided the products in good yields (31–61 %) with excellent stereoselectivities (80:20–93:7 dr, >99 % ee).
Ordered Nanoporous Thin Films by Nanosphere Lithography and Diazonium Electroreduction: Simple Elaboration of Ultra‐Micro‐Electrode Arrays
Authors: Nguyen Van‐Quynh , Schaming Delphine , Tran Dai Lam , Lacroix Jean‐Christophe
Published: October 2016

Highly ordered ultra‐micro‐electrode arrays are obtained using nanosphere lithography combined with electrochemical reduction of an aryl diazonium salt. A template made up of 2D hexagonally close‐packed polystyrene (PS) spheres was first deposited on indium tin oxide or glassy carbon substrates. Then, a thin layer of bisthienylbenzene (BTB) was grafted onto the interstices between the spheres. After dissolution of the PS spheres, the presence of micro‐hole arrays on the substrates was evidenced by atomic force microscopy. The electrochemical response of these micro‐hole arrays was investigated as a function of the size of the spheres used. Depending on their radius and the distance between adjacent holes, they behave as a partially blocked surface or as ultra‐microelectrode arrays (UMEAs).
Boosting High‐Rate Lithium Storage of V2O5 Nanowires by Self‐Assembly on N‐Doped Graphene Nanosheets
Authors: Gao Xiao‐Tian , Zhu Xiao‐Dong , Le Shi‐Ru , Yan Du‐Juan , Qu Cai‐Yu , Feng Yu‐Jie , Sun Ke‐Ning , Liu Yi‐Tao
Published: October 2016

The front cover artwork is provided by Xiao‐Tian Gao, Xiao‐Dong Zhu, and co‐workers, Harbin Institute of Technology (Harbin, P. R. China). The image shows that the nanohybrids synthesized by assembling V2O5 nanowires on N‐doped graphene nanosheets hold great promise as a cathode material for lithium‐ion batteries. Read the full text of the Communication at 10.1002/celc.201600305.
Structural and Conformational Aspects of Equatorial and Axial Trifluoromethyl, Difluoromethyl, and Monofluoromethyl Groups
Authors: Huchet Quentin A. , Schweizer W. Bernd , Kuhn Bernd , Carreira Erick M. , Müller Klaus
Published: October 2016

The X‐ray crystal structures of cis‐ and trans‐1‐(indol‐3‐yl)‐4‐methyl cyclohexane and its congeners with stepwise fluorination of the methyl group are reported. The trans‐configured compounds adopted diequatorial conformations, whereas the cis analogues adopted regular cyclohexane chair conformations with the methyl group preferentially assuming the axial position, even in the case of the CF3 group. Surprisingly, although the axial CF3 derivative displayed distinct valence deformations in the cyclohexane moiety, the observed structural changes were relatively modest. The cis derivatives with axial mono‐ and difluorinated methyl groups exhibited conformational disorder in the crystals with significant population levels for the staggered conformations that had one fluorine atom in the endo position; their respective trans counterparts adopted unique conformations, but again with one fluorine atom in the endo position. Theoretical calculations for a series of cis‐ and trans‐1,4‐dimethyl cyclohexane model compounds with stepwise fluorination of one equatorial or axial methyl group reproduced the experimentally observed structural response patterns very well, reproduced the experimentally determined nonlinear correlation of the axial–equatorial energy difference with the degree of methyl fluorination in a satisfactory manner, and provided further insights into important conformational aspects of partially fluorinated methyl groups.
The Relationship between NMR Chemical Shifts of Thermally Polarized and Hyperpolarized 89Y Complexes and Their Solution Structures
Authors: Xing Yixun , Jindal Ashish K. , Regueiro‐Figueroa Martín , Le Fur Mariane , Kervarec Nelly , Zhao Piyu , Kovacs Zoltan , Valencia Laura , Pérez‐Lourido Paulo , Tripier Raphaël , Esteban‐Gómez David , Platas‐Iglesias Carlos , Sherry A. Dean
Published: October 2016

Recently developed dynamic nuclear polarization (DNP) technology offers the potential of increasing the NMR sensitivity of even rare nuclei for biological imaging applications. Hyperpolarized 89Y is an ideal candidate because of its narrow NMR linewidth, favorable spin quantum number (I=
), and long longitudinal relaxation times (T1). Strong NMR signals were detected in hyperpolarized 89Y samples of a variety of yttrium complexes. A dataset of 89Y NMR data composed of 23 complexes with polyaminocarboxylate ligands was obtained using hyperpolarized 89Y measurements or 1H,89Y‐HMQC spectroscopy. These data were used to derive an empirical equation that describes the correlation between the 89Y chemical shift and the chemical structure of the complexes. This empirical correlation serves as a guide for the design of 89Y sensors. Relativistic (DKH2) DFT calculations were found to predict the experimental 89Y chemical shifts to a rather good accuracy.
Product Control using Substrate Design: Ruthenium‐Catalysed Oxidative C−H Olefinations of Cyclic Weinreb Amides
Authors: Das Riki , Kapur Manmohan
Published: October 2016

A new class of Weinreb amides has been developed as directing groups for the ruthenium‐catalysed regioselective oxidative C−H olefination. The new Weinreb amides successfully inhibit the N−O bond reductive cleavage usually associated with the cationic ruthenium system, thereby keeping intact the synthetic utility of Weinreb amides. Mechanistic studies reveal interesting aspects of the directing group capabilities of Weinreb amides when compared to simple amides of similar structures.
A Porphyrin‐Based Porous rtl Metal–Organic Framework as an Efficient Catalyst for the Cycloaddition of CO2 to Epoxides
Authors: Jiang Wei , Yang Jin , Liu Ying‐Ying , Song Shu‐Yan , Ma Jian‐Fang
Published: October 2016

A porous rtl metal–organic framework (MOF) [Mn5L(H2O)6⋅(DMA)2]⋅5DMA⋅4C2H5OH (1⋅Mn) (H10L=5,10,15,20‐tetra(4‐(3,5‐dicarboxylphenoxy)phenyl)porphyrin; DMA=N,N′‐dimethylacetamide) was synthesized by employing a new porphyrin‐based octacarboxylic acid ligand. 1⋅Mn exhibits high MnII density in the porous framework, providing it great Lewis‐acid heterogeneous catalytic capability for the cycloaddition of CO2 with epoxides. Strikingly, 1⋅Mn features excellent catalytic activity to the cycloaddition of CO2 to epoxides, with a remarkable initial turnover frequency 400 per mole of catalyst per hour at 20 atm. As‐synthesized 1⋅Mn also exhibits size selectivity to different epoxide substrates on account of their steric hindrance. The high catalytic activity, size selectivity, and stability toward the epoxides on catalytic cycloaddition of CO2 make 1⋅Mn a promising heterogeneous catalyst for fixation and utilization of CO2.
[FeFe]‐Hydrogenase H‐Cluster Mimics with Unique Planar μ‐(SCH2)2ER2 Linkers (E=Ge and Sn)
Authors: Abul‐Futouh Hassan , Almazahreh Laith R. , Sakamoto Takahiro , Stessman Nhu Y. T. , Lichtenberger Dennis L. , Glass Richard S. , Görls Helmar , El‐Khateeb Mohammad , Schollhammer Philippe , Mloston Grzegorz , Weigand Wolfgang
Published: October 2016

Analogues of the [2Fe‐2S] subcluster of hydrogenase enzymes in which the central group of the three‐atom chain linker between the sulfur atoms is replaced by GeR2 and SnR2 groups are studied. The six‐membered FeSCECS rings in these complexes (E=Ge or Sn) adopt an unusual conformation with nearly co‐planar SCECS atoms perpendicular to the Fe‐Fe core. Computational modelling traces this result to the steric interaction of the Me groups with the axial carbonyls of the Fe2(CO)6 cluster and low torsional strain for GeMe2 and SnMe2 moieties owing to the long C−Ge and C−Sn bonds. Gas‐phase photoelectron spectroscopy of these complexes shows a shift of ionization potentials to lower energies with substantial sulfur orbital character and, as supported by the computations, an increase in sulfur character in the predominantly metal–metal bonding HOMO. Cyclic voltammetry reveals that the complexes follow an ECE‐type reduction mechanism (E=electron transfer and C=chemical process) in the absence of acid and catalysis of proton reduction in the presence of acid. Two cyclic tetranuclear complexes featuring the sulfur atoms of two Fe2S2(CO)6 cores bridged by CH2SnR2CH2, R=Me, Ph, linkers were also obtained and characterized.
Systematic Modulation of the Fluorescence Brightness in Boron‐Dipyrromethene (BODIPY)‐Tagged N‐Heterocyclic Carbene (NHC)–Gold–Thiolates
Authors: Halter Oliver , Vasiuta Roman , Fernández Israel , Plenio Herbert
Published: October 2016

Five different highly fluorescent boron‐dipyrromethene (BODIPY)‐tagged N‐heterocyclic carbene NHC–gold halide complexes were synthesized. The substitution of the halogeno ligand by 4‐substituted aryl thiolates leads to a decrease in the brightness of the complexes. This decrease depends on the electronic nature of the thiols, being most pronounced with highly electron‐rich thiols (4‐R=NMe2). The brightness of the gold thiolates also depends on the distance between the sulfur atom and the BODIPY moiety. The systematic variation of the electron density of [(NHC–bodipy)Au(SC6H4R)] (via different R groups) enables the systematic variation of the fluorescence brightness of an appended BODIPY fluorophore. Based on this and supported by DFT calculations, a photoinduced electron‐transfer quenching appears to be the dominant mechanism controlling the brightness of the appended BODIPY dye.
Two‐State Reactivity of Histone Demethylases Containing Jumonji‐C Active Sites: Different Mechanisms for Different Methylation Degrees
Authors: Alberro Nerea , Torrent‐Sucarrat Miquel , Arrastia Iosune , Arrieta Ana , Cossío Fernando P.
Published: October 2016

The N‐demethylation reactions of N,N,N‐trimethylpropan‐1‐ammonium and N,N‐dimethyl‐ and N‐methylpropan‐1‐aminium cations in the presence of [(AcO)2(imidazole)2(H2O)Fe=O] complex have been studied by density functional theory. These transformations are suitable models for the N‐demethylation of tri‐, di‐, and monomethylated lysine residues of histones in the presence of Jumonji‐C containing histone demethylases. It has been found that the N‐demethylation reaction is stepwise and occurs on triplet and quintet potential energy hypersurfaces. Both spin states are nearly degenerated and the quantum jump from one state to another has a transition probability close to one. The preferred intrinsic mechanism depends upon the methylation degree. For trimethylated residues the mechanism consists of a proton abstraction from a methyl group followed by a formation of a hydroxymethylaminium intermediate. This mechanism also occurs when dimethylated residues are able to orientate one methyl group towards the Fe=O group of the catalytic site. In contrast, when a N−H group of the substrate is close enough to the Fe=O group, the intrinsically preferred N‐demethylation reaction leads to the formation of an iminium intermediate that can be hydrolyzed to form the corresponding N‐demethylated product.
A Systematic Account on Aromatic Hydroxylation by a Cytochrome P450 Model Compound I: A Low‐Pressure Mass Spectrometry and Computational Study
Authors: Cantú Reinhard Fabián G. , Sainna Mala A. , Upadhyay Pranav , Balan G. Alex , Kumar Devesh , Fornarini Simonetta , Crestoni Maria Elisa , de Visser Sam P.
Published: October 2016

Cytochrome P450 enzymes are heme‐containing mono‐oxygenases that mainly react through oxygen‐atom transfer. Specific features of substrate and oxidant that determine the reaction rate constant for oxygen atom transfer are still poorly understood and therefore, we did a systematic gas‐phase study on reactions by iron(IV)‐oxo porphyrin cation radical structures with arenes. We present herein the first results obtained by using Fourier transform‐ion cyclotron resonance mass spectrometry and provide rate constants and product distributions for the assayed reactions. Product distributions and kinetic isotope effect studies implicate a rate‐determining aromatic hydroxylation reaction that correlates with the ionization energy of the substrate and no evidence of aliphatic hydroxylation products is observed. To further understand the details of the reaction mechanism, a computational study on a model complex was performed. These studies confirm the experimental hypothesis of dominant aromatic over aliphatic hydroxylation and show that the lack of an axial ligand affects the aliphatic pathways. Moreover, a two‐parabola valence bond model is used to rationalize the rate constant and identify key properties of the oxidant and substrate that drive the reaction. In particular, the work shows that aromatic hydroxylation rates correlate with the ionization energy of the substrate as well as with the electron affinity of the oxidant.
Chemical Non‐Innocence of an Aliphatic PNP Pincer Ligand
Authors: Schneck Felix , Finger Markus , Tromp Moniek , Schneider Sven
Published: October 2016

The synthesis of the divinylamido PNP nickel(II) complex [NiBr{N(CHCHPtBu2)2}] is reported. This compound exhibits reversible, ligand‐centered oxidation and protonation reactions. The resulting pincer chemical non‐innocence can be utilized for benzylic C−H hydrogen atom abstraction. The thermochemistry and kinetics of hydrogen atom transfer were examined.
Ru‐Catalyzed Dehydrogenative C−O Bond Formation with Anilines and Phenols
Authors: Heitz Christophe , Jones Alexander W. , Oezkaya Bünyamin S. , Bub Christina L. , Louillat‐Habermeyer Marie‐Laure , Wagner Victoria , Patureau Frederic W.
Published: October 2016

The Ru catalyzed cross‐dehydrogenative C−O bond formation between anilines and phenols is described and discussed. The exclusive C−O versus C−N bond‐formation selectivity, moreover in the absence of chelating–assisting directing groups and while leaving the N−H position untouched, is a remarkable feature of this metal‐catalyzed radical cross‐dehydrogenative coupling.
ChemInform Abstract: Crystal Structure of Ag2(μ‐SCN)2(NH3)4.
Authors: Mueller Thomas G. , Kraus Florian
Published: October 2016

Colorless crystals of the title compound are obtained by reacting solid AgSCN with anhydrous liquid NH3 (237 K, 2 weeks).
ChemInform Abstract: Li2GeMo3O8: A Novel Reduced Molybdenum Oxide Containing Mo3O13 Cluster Units.
Authors: Gall Philippe , Gougeon Patrick
Published: October 2016

Single crystals of the title compound are prepared by solid state reaction of a stoichiometric mixture of Li2MoO4, GeO2, MoO3, and Mo (arc‐welded Mo crucible under reduced Ar pressure, 1923 K, 72 h).
ChemInform Abstract: Two New Lanthanide Members of Francisite Family Cu3Ln(SeO3)2O2Cl (Ln: Eu, Lu).
Authors: Zakharov K. V. , Zvereva E. A. , Kuznetsova E. S. , Berdonosov P. S. , Dolgikh V. A. , Markina M. M. , Olenev A. V. , Shakin A. A. , Volkova O. S. , Vasiliev A. N.
Published: October 2016

Polycrystalline Cu3Eu(SeO3)2O2Cl and Cu3Lu(SeO3)2O2Cl are prepared by solid state reaction of Eu2O3 (Lu2O3), CuO, CuCl2, and SeO2 (evacuated quartz tubes, 1.
ChemInform Abstract: Fluorine‐Doped Antiperovskite Electrolyte for All‐Solid‐State Lithium‐Ion Batteries.
Authors: Goodenough John B.
Published: October 2016

Li2(OH)0.9F0.1Cl is prepared by melting mixtures of Li2O, LiOH, and LiX (X: Cl, F) at 350 °C for 0.5—1 h.
ChemInform Abstract: The Application of N‐Protected 3‐Vinylindoles in Chiral Phosphoric Acid‐Catalyzed [3 + 2] Cyclization with 3‐Indolylmethanols: Monoactivation of the Catalyst to Vinyliminium.
Authors: Fan Tao , Zhang Hong‐Hao , Li Can , Shen Yang , Shi Feng
Published: October 2016

The enantioselective [3 + 2] cycloaddition of isatin‐derived 3‐indolylmethanols with 3‐vinylindoles is optimized with respect to the BINOL‐type phosphonic acid catalyst and the reaction solvent.
ChemInform Abstract: MOF‐253‐Pd(OAc)2: A Recyclable MOF for Transition‐Metal Catalysis in Water.
Authors: Van Zeeland Ryan , Li Xinle , Huang Wenyu , Stanley Levi M.
Published: October 2016

The new reusable catalyst is utilized in conjugate addition reactions of arylboronic acids to β,β‐disubstituted enones in aqueous media.
ChemInform Abstract: Enantio‐ and Diastereoselective Desymmetrization of α‐Alkyl‐α‐diazoesters by Dirhodium(II)‐Catalyzed Intramolecular C—H Insertion.
Authors: Miyazawa Taku , Minami Kazushi , Ito Motoki , Anada Masahiro , Matsunaga Shigeki , Hashimoto Shunichi
Published: October 2016

The title reaction proceeds best in the presence of the Rh catalyst shown to form bicyclic ring systems with at least one cyclopentane unit in an enantio‐ and diastereoselective manner.
ChemInform Abstract: Dipeptide‐Derived Multifunctional Phosphonium Salt as a Catalyst to Synthesize Highly Functionalized Chiral Cyclopentanes.
Authors: Lu Yingpeng , Cao Dongdong , Zhang Jiaxing , Wang Hongyu , Zou Gang , Zhao Gang
Published: October 2016

The reaction affords cyclopentane structures with 3 contiguous stereocenters and a quaternary carbon atom.
ChemInform Abstract: Preparation of Enantiomerically Enriched Aromatic β‐Hydroxynitriles and Halohydrins by Ketone Reduction with Recombinant Ketoreductase KRED1‐Pglu.
Authors: Contente Martina L. , Serra Immacolata , Molinari Francesco , Gandolfi Raffaella , Pinto Andrea , Romano Diego
Published: October 2016

Various types of ketone substrates can be efficiently reduced in the presence of the title enzyme, isolated from P.
ChemInform Abstract: A New Synthetic Strategy to 2,3‐Diallyl‐1,4‐quinones via One‐Pot Double Claisen Rearrangement and Retro Diels—Alder Reaction.
Authors: Kotha Sambasivarao , Gunta Rama
Published: October 2016

A simple alternative method to 2,3‐diallyl‐1,4‐quinone derivatives via a one‐pot double claisen rearrangement and retro Diels—Alder reaction sequence involving readily available starting materials is reported.
ChemInform Abstract: One‐Pot Three Component Synthesis of 3,5‐Disubstituted 2,6‐Dicyanoaniline Derivatives Using 4‐Dimethylaminopyridine (DMAP) as a Catalyst.
Authors: Bhattacharjee Suchandra , Khan Abu T.
Published: October 2016

An improved methodology for the construction of densely substituted benzene, from a wide variety of aldehydes, malononitrile, and β‐nitro‐olefins by using a nucleophilic catalyst DMAP is designed.
ChemInform Abstract: Heterogeneous Copper‐Catalyzed Aerobic Oxidative Conversions of Benzaldehydes with Aqueous Ammonia to Give Benzonitriles.
Authors: Yoon Yousun , Kim Bo Ram , Lee Chang Yeon , Kim Jinho
Published: October 2016

Pyrolysis of copper(II) 1,3,5‐benzenetricarboxylate provides a heterogeneous copper catalyst, which is successfully employed for the synthesis of benzonitriles from benzaldehydes.
ChemInform Abstract: Switchable [3 + 2] and [4 + 2] Heteroannulation of Primary Propargylamines with Isonitriles to Imidazoles and 1,6‐Dihydropyrimidines: Catalyst Loading Enabled Reaction Divergence.
Authors: Tong Shuo , Wang Qian , Wang Mei‐Xiang , Zhu Jieping
Published: October 2016

A simple switch in the catalyst loading under otherwise identical conditions allows the preparation of either the pyrazole or dihydropyrimidine skeleton, represented by polysubstituted derivatives.
ChemInform Abstract: Asymmetric Synthesis of Pyrano[2,3‐c]pyrazoles via a Cascade Reaction Between Morita—Baylis—Hillman Acetates of Nitroalkenes and Pyrazolones.
Authors: Xie Jin , Sha Feng , Wu Xin‐Yan
Published: October 2016

Optimized conditions A) allow the preparation of the pharmaceutically important scaffold with excellent enantio‐ and diastereoselectivity.
ChemInform Abstract: Transition Metal Free Intramolecular Approach for the Synthesis of Cyclopenta[b]chromene Derivatives from Phenol Substituted Fulvene Derived Azabicyclic Olefins.
Authors: Vijayan Ajesh , Baiju T. V. , Varughese Sunil , Radhakrishnan K. V.
Published: October 2016

A versatile route for the synthesis of cyclopentene fused chromenes via base catalyzed transformation of phenol substituted fulvene derived azabicyclic olefins is described.
ChemInform Abstract: Metal‐Free Synthesis of Highly Substituted Quinolines under Mild Conditions.
Authors: Natarajan Rakesh , Unnikrishnan Peruparambil A. , Radhamani Sandhya , Rappai John P. , Prathapan Sreedharan
Published: October 2016

Starting from easily accessible nitrones and acetylenes, a simple, metal free synthesis of substituted quinolines under mild conditions with high atom efficiency is developed.
ChemInform Abstract: Rapid and Efficient Cascade Synthesis of 2‐Amino‐4(3H)‐quinazolinones over an in situ‐Generated Heterogeneous CuCO3—K2CO3 Nanocomposite.
Authors: Thakur Maheshwar S. , Nayal Onkar S. , Bhatt Vinod , Sharma Sushila , Kumar Neeraj
Published: October 2016

The nanocomposite catalyzed cascade reaction of 2‐halobenzoic acids and guanidines or amidines proceeds rapidly in air without the addition of a ligand or additive to form quinazoline derivatives.
ChemInform Abstract: Copper‐Catalyzed C—H Oxygenation of Benzoxepine‐4‐carboxylates: Facile Synthesis and Photophysical Properties of Naphtho[2,1‐d]oxazoles and Benzo[c]phenoxazines.
Authors: Prasad Kasagani Veera , Saidachary Gannerla , Hariprasad Kurma Siva , Nagaraju Peethani , Rao Vaidya Jayathirtha , Raju Bhimapaka China
Published: October 2016

A solvent‐free one‐pot protocol is developed for the reaction of oxepine derivatives (I) with anilines and benzylamine to afford benzophenoxazines and naphthooxazoles.
ChemInform Abstract: Synthesis of Pyrrolo[2,1‐f][1,2,4]triazin‐4(3H)‐ones: Rearrangement of Pyrrolo[1,2‐d][1,3,4]oxadiazines and Regioselective Intramolecular Cyclization of 1,2‐Biscarbamoyl‐substituted 1H‐Pyrroles.
Authors: Son Kkonnip , Park Seong Jun
Published: October 2016

Regioselective intramolecular cyclization of pyrrole substrates (I) provide pyrrolooxadiazines (II) which undergo rearrangement to form pyrrolotriazines (III).
ChemInform Abstract: Dynamic Kinetic Resolution Approach for the Asymmetric Synthesis of Tetrahydrobenzodiazepines Using Transfer Hydrogenation by Chiral Phosphoric Acid.
Authors: Horiguchi Kosaku , Yamamoto Eri , Saito Kodai , Yamanaka Masahiro , Akiyama Takahiko
Published: October 2016

Dihydrobenzodiazepines or benzodiazepines bearing aryl substituents at the 2‐ and 4‐position of the heterocyclic part are transformed to the chiral title compounds in the presence of BNPA using different amounts of the hydrogen transfer reagent BTA.
ChemInform Abstract: Total Synthesis of (.+‐.)‐Lingzhilactone B via Semipinacol Rearrangement.
Authors: Chen Dong , Li Xiao‐Mei , Liu Hao‐Miao , Li Ming‐Ming , Cheng Yong‐Xian , Qin Hong‐Bo
Published: October 2016

The first total synthesis of the title compound (I) is described.
ChemInform Abstract: A New Method of Synthesis and Characterization of Nano‐Sized Mercuric Iodide by Solid‐Gas Reaction.
Authors: Agrawal Namita Rani , Fredrick Shobna Dorthy , Das Ishwar
Published: October 2016

Nanocrystalline HgI2 (7—52 nm) is prepared by solid gas reaction of Hg2(NO3)2 and I2 vapor either in glass capillaries, on microslides, or in a specifically designed glass channel (35 °C).
ChemInform Abstract: Face the Edges: Catalytic Active Sites of Nanomaterials
Authors: Ni Bing , Wang Xun
Published: October 2016

Review: 218 refs.
ChemInform Abstract: Mn‐, Fe‐, and Co‐Catalyzed Radical Hydrofunctionalizations of Olefins
Authors: Crossley Steven W. M. , Obradors Carla , Martinez Ruben M. , Shenvi Ryan A.
Published: October 2016

Review: 476 refs.
ChemInform Abstract: Catalytic Hydroamination of Unsaturated Hydrocarbons
Authors: Isaeva Vera I. , Kustov Leonid M.
Published: October 2016

Review: 109 refs.
ChemInform Abstract: A Concise Enantioselective Synthesis of (+)‐L‐733,060 and (+)‐T‐2328 via Sequential Proline Catalysis.
Authors: Lalwani Komal G. , Sudalai Arumugam
Published: October 2016

(+)‐L‐733,060 (I) is obtained by an asymmetric synthesis in 6 steps with an overall yield of 32% (93% e.e.) and (+)‐T‐2328 (II) in 10 steps with 28% overall yield (93% e.e.).
Effect of gravity orientation in the study of thermodiffusion
Authors: Mousavi Seyyed Arash , Yousefi Tooraj , Saghir Ziad
Published: October 2016

This paper describes the measurement of the Soret coefficient of a hydrocarbon binary liquid mixture at different orientations to the gravity vector. The working fluid in the experiment was composed of 1,2,3,4‐tetrahydronaphtalene (THN) and dodecane (C12) at mass fractions of 0.50/0.50 and a temperature of 298.15 K. The experimental technique used in this study was an optical digital interferometry method using a Mach‐Zehnder Interferometer. A fast Fourier transform method was used for image processing. The experimental approach was supplemented with a numerical solution using the finite volume method. Experimental and numerical results both confirmed that cell inclination during the thermodiffusion process had a tremendous effect on the measurement of the Soret coefficient.
Crystallization behaviour and lamellar thickness distribution of metallocene‐catalyzed polymer: Effect of 1‐alkene comonomer and branch length
Authors: Daud Muhammad , Shehzad Farrukh , Al‐Harthi Mamdouh A.
Published: October 2016

The effect of comonomer and branching on the melt crystallization and lamellar thickness distribution was studied for ethylene and 1‐alkene copolymers. The comonomers used in this study are 1‐hexene, 1‐octene, and 1‐decene. A notable influence of the comonomer ratio in the feed was observed on the crystallization and melting behaviour. The Ozawa and Mo models were found suitable for these copolymers. However, variation of relative crystallinity at different heating rates preferred the Mo method over the Ozawa method. The melting behaviour and lamellar thickness distribution of the copolymers were analyzed by the help of the modified Gibbs‐ Thomson equation. The activation energies (EA) for the melt crystallization were calculated using the Kissinger method. It was observed that 1‐hexene comonomer exhibits lower EA, indicating an easier crystallization process as compared to other comonomers used. Overall, crystallization was found to be more influenced by the degree of branching rather than the comonomer type.
Microencapsulation of astaxanthin in alginate using modified emulsion technology: Preparation, characterization, and cytostatic activity
Authors: Zhang Xiujuan , Yin Wenjuan , Qi Yankai , Li Xiangcun , Zhang Wenjun , He Gaohong
Published: October 2016

In the present study, astaxanthin was microencapsulated in a biodegradable material, calcium alginate, using a modified emulsion technology developed at our laboratory. The modified emulsion method involves the reaction between a sodium alginate emulsion and a calcium chloride emulsion. After mixing these emulsions, Ca2+ penetrates two oil‐water layers to combine −COO‐, and microparticles are formed with narrow size distribution and good dispersion due to the mild reaction speed. The microencapsulated astaxanthin showed much higher storage stability and antioxidant activity than the non‐encapsulated astaxanthin. Cytostatic activity was preliminarily evaluated on adipose‐derived stem cells, the microencapsulated astaxanthin showed significant cytostatic activity due to the improved solubility of astaxanthin caused by the good biocompatibility of calcium alginate. Characterization confirmed the existence of microparticles with high encapsulation efficiency (more than 85 %), uniform size distribution (1.61 µm), and sustained astaxanthin release, suggesting the prepared microparticles by the modified emulsion method have great potential in pharmaceutical, food, and cosmetic industries.