bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Sequential Method to Prepare Polymorphs and Solvatomorphs of [Fe(1,3‐bpp)2](ClO4)2⋅nH2O (n=0, 1, 2) with Varying Spin‐Crossover Behaviour
Authors: Bartual‐Murgui Carlos , Codina Carlota , Roubeau Olivier , Aromí Guillem 
Published: August 2016

AbstractTwo polymorphs of the spin crossover (SCO) compound [Fe(1,3‐bpp)2](ClO4)2 (1 and 2; 1,3‐bpp=2‐(pyrazol‐1‐yl)‐6‐(pyrazol‐3‐yl)pyridine) were prepared using a novel, stepwise procedure. Crystals of 1 deposit from dry solvents, while 2 is obtained from a solid‐state procedure, by sequentially removing lattice H2O molecules from the solvatomorph [Fe(1,3‐bpp)2](ClO4)2⋅2 H2O (2⋅2 H2O), using single‐crystal‐to‐single‐crystal (SCSC) transformations. Hydrate 2⋅2 H2O is obtained through the same reaction as 1, now with 2.5 % of water added. Compounds 2 and 2⋅2 H2O are unstable in the atmosphere and absorb or lose one equivalent of water, respectively, to both yield the stable solvatomorph [Fe(1,3‐bpp)2](ClO4)2⋅H2O (2⋅H2O), also following SCSC processes. The four derivatives have been characterised by single‐crystal X‐ray diffraction (SCXRD). Furthermore, the homogeneity of the various compounds as well as their SCSC interconversions have been confirmed by powder X‐ray diffraction (PXRD). Polymorphs 1 and 2 exhibit abrupt SCO behaviour near room temperature with T1/2↑=279/316 K and T1/2↓=276/314 K (near 40 K of shift) and different cooperativity.
Communication between Discrete Nanostructures Triggered by Fine Tuning of an External Stimulus
Authors: Schilirò Matteo , Contino Annalinda , Millesi Salvatrice , Maccarrone Giuseppe , Gulino Antonino 
Published: August 2016

AbstractThe design of molecular architectures able to transfer mass to each other is a field of extreme importance. In the present study it is shown that two especially designed covalently assembled nanostructures can interchange Cu2+ ions upon an external OH− trigger. The obtained solid interfaces are of interest for signaling, communication, memory storage and optical devices.
Synthesis of an Open‐Cage Structure POSS Containing Various Functional Groups and Their Effect on the Formation and Properties of Langmuir Monolayers
Authors: Dutkiewicz Michał , Karasiewicz Joanna , Rojewska Monika , Skrzypiec Marta , Dopierała Katarzyna , Prochaska Krystyna , Maciejewski Hieronim 
Published: August 2016

AbstractRecently, silsesquioxanes have been recognized as a new group of film‐forming materials. This study has been aimed at determining the effect of the kind of functional groups present in two different open‐cage structure POSS molecules on the possibility of the formation of Langmuir monolayers and their properties. To achieve this goal, two new POSS derivatives (of open‐cage structures) containing polyether and fluoroalkyl functional groups have been synthesized on the basis of a hydrosilylation process. An optimization of the process was performed, which makes it possible to obtain the above‐mentioned derivatives with high yields. In the next step, the Langmuir technique was applied to measurements of the surface pressure (π) − the mean molecular area (A) isotherms during the compression of monolayers formed by molecules of the two POSS derivatives considered. Subsequently, the monolayers were transferred onto quartz plates according to the Langmuir–Blodgett technique. Both derivatives are able to form insoluble Langmuir films at the air–water interface, which can be transferred onto a solid substrate and effectively change its wetting properties.
Palladium‐Catalyzed N‐Arylation of Iminodibenzyls and Iminostilbenes with Aryl‐ and Heteroaryl Halides
Authors: Huang Wenliang , Buchwald Stephen L. 
Published: August 2016

AbstractCompounds containing the iminodibenzyl and iminostilbene ring systems are prevalent in medicinal targets and functional materials. Herein, we report palladium‐catalyzed conditions for the N‐arylation of these ring systems. This protocol could be applied to a variety of (hetero)aryl chloride and bromide substrates, including ones, which are sterically hindered or those containing a variety of functional groups. Use of the fourth‐generation palladacycle precatalyst gave good to excellent yields by using low palladium‐catalyst loadings (0.1 to 1 mol %).
Pd‐PEPPSI‐IHeptCl: A General‐Purpose, Highly Reactive Catalyst for the Selective Coupling of Secondary Alkyl Organozincs
Authors: Atwater Bruce , Chandrasoma Nalin , Mitchell David , Rodriguez Michael J. , Organ Michael G. 
Published: August 2016

AbstractDichloro[1,3‐bis(2,6‐di‐4‐heptylphenyl)imidazol‐2‐ylidene](3‐chloropyridyl)palladium(II) (Pd‐PEPPSI‐IHeptCl), a new, very bulky yet flexible Pd–N‐heterocyclic carbene (NHC) complex has been evaluated in the cross‐coupling of secondary alkylzinc reactants with a wide variety of oxidative addition partners in high yields and excellent selectivity. The desired, direct reductive elimination branched products were obtained with no sign of migratory insertion across electron‐rich and electron‐poor aromatics and all forms of heteroaromatics (five and six membered). Impressively, there is no impact of substituents at the site of reductive elimination (i.e., ortho or even di‐ortho), which has not yet been demonstrated by another catalyst system to date.
Identification of Highly Potent Protein Kinase C‐Related Kinase 1 Inhibitors by Virtual Screening, Binding Free Energy Rescoring, and in vitro Testing
Authors: Slynko Inna , Schmidtkunz Karin , Rumpf Tobias , Klaeger Susan , Heinzlmeir Stephanie , Najar Abdulkarim , Metzger Eric , Kuster Bernhard , Schüle Roland , Jung Manfred , Sippl Wolfgang 
Published: August 2016

AbstractDespite the considerable interest in protein kinase C‐related kinase 1 (PRK1) as a target in cancer research, there is still a lack of PRK1 inhibitors with suitable selectivity profiles and physicochemical properties. To identify new PRK1 inhibitors we applied a virtual screening approach, which combines ensemble docking, minimization of the protein–ligand complex, binding free energy calculations, and application of quantitative structure–activity relationship (QSAR) models for predicting in vitro activity. The developed approach was then applied in a prospective manner to screen available libraries of kinase inhibitors from Selleck and GlaxoSmithKline (GSK). Compounds that showed favorable prediction were then tested in vitro for PRK1 inhibition. Some of the hits were found to inhibit PRK1 in the low‐nanomolar range. Three in vitro hits were additionally tested in a mass‐spectrometry‐based cellular kinase profiling assay to examine selectivity. Our findings show that nanomolar and drug‐like inhibitors can be identified by the virtual screening approach presented herein. The identified inhibitors are valuable tools for gaining a better understanding of PRK1 inhibition, and the identified hits can serve as starting points for further chemical optimization.
Frequency of psycho‐oncologic and social service counseling in cancer centers relative to center site and hospital characteristics: Findings from 879 center sites in Germany, Austria, Switzerland, and Italy
Authors: Kowalski Christoph , Ferencz Julia , Singer Susanne , Weis Ilse , Wesselmann Simone 
Published: August 2016

BACKGROUNDThere is extensive evidence that patients with cancer and cancer survivors have a strong need for expert support in relation to the psychological and social consequences of the disease. The requirements set out in the German Cancer Society's cancer center certification system include the routine provision of psycho‐oncologic care (POC) and social service counseling for every patient. The current study investigated which organizational and structural characteristics in hospitals account for variations in psychosocial care provision in these centers.METHODSData routinely collected during the certification process regarding the percentages of psychosocial care provision and characteristics of center sites and hospitals were matched with data with regard to size of the municipality, teaching hospital status, and institutional ownership. Linear multilevel regression analyses were performed to identify the characteristics of hospitals and center sites that were related to psychosocial care provision.RESULTSSubstantial differences were found for different types of cancer (eg, a greater provision of psychosocial care in centers specializing in breast rather than prostate cancer). There was more POC provision in longer‐certified centers and less in rural areas and university hospitals. Much of the variation between hospitals remains unexplained.CONCLUSIONSAlthough the implementation of mandatory psychosocial services generally provides patients with access to POC and social service counseling, the wide differences in the provision of counseling indicate that additional measures are needed to avoid inequalities resulting from the center at which a patient receives cancer treatment. Cancer 2016;122:3538–3545. © 2016 American Cancer Society
Expression of homeobox genes in the mouse olfactory epithelium
Authors: Parrilla Marta , Chang Isabelle , Degl'Innocenti Andrea , Omura Masayo 
Published: August 2016

AbstractHomeobox genes constitute a large family of genes widely studied because of their role in the establishment of the body pattern. However, they are also involved in many other events during development and adulthood. The main olfactory epithelium (MOE) is an excellent model to study neurogenesis in the adult nervous system. Analyses of homeobox genes during development show that some of these genes are involved in the formation and establishment of cell diversity in the MOE. Moreover, the mechanisms of expression of odorant receptors (ORs) constitute one of the biggest enigmas in the field. Analyses of OR promoters revealed the presence of homeodomain binding sites in their sequences. Here we characterize the expression patterns of a set of 49 homeobox genes in the MOE with in situ hybridization. We found that seven of them (Dlx3, Dlx5, Dlx6, Msx1, Meis1, Isl1, and Pitx1) are zonally expressed. The homeobox gene Emx1 is expressed in three guanylate cyclase+ populations, two located in the MOE and the third one in an olfactory subsystem known as Grüneberg ganglion located at the entrance of the nasal cavity. The homeobox gene Tshz1 is expressed in a unique patchy pattern across the MOE. Our findings provide new insights to guide functional studies that aim to understand the complexity of transcription factor expression and gene regulation in the MOE. J. Comp. Neurol. 524:2713–2739, 2016. © 2016 Wiley Periodicals, Inc.
Effect of Anionic Electrolytes and Precursor Concentrations on the Electrodeposited Pt Structures
Authors: Kim Dajeong , Kim Jongwon 
Published: August 2016

AbstractElectrodeposition of functional metal surfaces has received great attention because of their useful applications. Recently, interesting electrodeposition behavior of Pt at −0.8 V (vs. Ag/AgCl) was reported, where underpotential deposited H (Hupd) layers played a unique role in the electrodeposition. Here, we report the effect of anionic electrolytes and precursor concentrations on the electrochemical deposition behavior of Pt. Depending on these two experimental parameters, two distinct Pt structures, monolayer Pt films and Pt spheres, were electrodeposited at −0.8 V. In addition to the underpotential deposited H (Hupd) layers formed at −0.8 V, the adsorption of Cl− also plays a significant role in determining the electrodeposited Pt structures. When the PtCl42− concentration was low and the Cl− concentration was high enough for the adsorption of PtCl42− to be blocked by the Hupd and Cl− layers, monolayer Pt films were electrodeposited. Otherwise, further electrodeposition of Pt spheres over the monolayer Pt films occurred. The effect of other halide ion adsorption and the controlled growth of Pt spheres during the Pt electrodeposition were also investigated. The electrochemical deposition behavior of Pt demonstrated in this work provides insight into the fabrication of functional Pt surfaces.
Ultra‐sensitive, rapid gold nanoparticle‐quantum dot plexcitonic self‐assembled aptamer‐based nanobiosensor for the detection of human cardiac troponin I
Authors: Rezaei Zahra , Ranjbar Bijan 
Published: August 2016

Acute myocardial infarction (AMI) is one of the leading causes of death throughout the world. Usual methods for detecting AMI are expensive, time‐consuming and using blood samples as biological samples. Therefore, creating an ultra‐fast, sensitive and non‐invasive diagnostic test is necessary. Herein, a novel ultra‐sensitive, fluorescent, plasmon‐exciton coupling hybrid of a gold nanoparticle‐quantum dot (PQ)‐based aptamer nanobiosensor is presented for the detection of human cardiac troponin I (cTnI), the golden biomarker of AMI, and a preclinical test is performed within saliva. The binding of the cTnI protein to aptamer leads to a fluorescence enhancement of the plexcitonic hybrid system. The response range of this nanobiosensor is 0.4–2500 fM and the limit of detection is 0.3 fM. It seems that this novel design of nanobiosensor in the form of the PQ plexcitonic hybrid system can presents new opportunities for nanobiosensor progress.
Redox Signaling through DNA
Authors: O'Brien Elizabeth , Silva Rebekah M. B. , Barton Jacqueline K. 
Published: August 2016

AbstractBiological electron transfer reactions between metal cofactors are critical to many essential processes within the cell. Duplex DNA is, moreover, capable of mediating the transport of charge through its π‐stacked nitrogenous bases. Increasingly, [4Fe4S] clusters, generally redox‐active cofactors, have been found to be associated with enzymes involved in DNA processing. DNA‐binding enzymes containing [4Fe4S] clusters can thus utilize DNA charge transport (DNA CT) for redox signaling to coordinate reactions over long molecular distances. In particular, DNA CT signaling may represent the first step in the search for DNA lesions by proteins containing [4Fe4S] clusters that are involved in DNA repair. Here we describe research carried out to examine the chemical characteristics and biological consequences of DNA CT. We are finding that DNA CT among metalloproteins represents powerful chemistry for redox signaling at long range within the cell.
Metalloneurochemistry and the Pierian Spring: ‘Shallow Draughts Intoxicate the Brain’
Authors: Goldberg Jacob M. , Loas Andrei , Lippard Stephen J. 
Published: August 2016

AbstractMetal ions perform critical and diverse functions in nervous system physiology and pathology. The field of metalloneurochemistry aims to understand the mechanistic bases for these varied roles at the molecular level. Here, we review research that illustrates progress toward achieving this ambitious goal and identify key challenges for the future. We examine the use of lithium as a mood stabilizer, the roles of mobile zinc and copper in the synapse, the interplay of nitric oxide and metals in retrograde signaling, and the regulation of iron homeostasis in the brain. We are beginning to uncover the principles by which receptors and transmitters utilize metal ions to modulate neurotransmission. These advances have revealed exciting new insights into the intricate mechanisms that give rise to learning, memory, and sensory perception, while opening many new avenues for further exploration.
Novel Electrochemically Treated Graphite Pencil Electrode Surfaces for the Determination of Traceα‐Naphthol in Water Samples
Authors: Rana Azeem , Kawde Abdel‐Nasser 
Published: August 2016

AbstractAn electrochemically treated graphite pencil electrode (PGPE) has been simply prepared for trace level determination of α‐naphthol. The pretreatment of GPE surfaces is conducted in 0.8 M NaOH by cycling the potential between +1.3 and +1.9 V for 50 CV segments at a scan rate of 100 mV s−1. The influence of the pretreatment is studied extensively, and optimum conditions are obtained. Linear sweep anodic stripping voltammetry (LSASV) is used for the determination of α‐naphthol. Based on the constructed calibration curve, a linear range of 0.01 μM to 2.0 μM with a detection limit of 1.5 nM (S/N=3) is obtained. The results reveal that the electrochemical treatment of the GPE surface improves its electrochemical catalytic activity with reference to surfaces of the non‐treated GPE. The present method is applied for the determination of trace α‐naphthol in real water samples.
Maternal PTSD and Children's Adjustment: Parenting Stress and Emotional Availability as Proposed Mediators
Authors: Samuelson Kristin W. , Wilson Christina K. , Padrón Elena , Lee Suellen , Gavron Lauren 
Published: August 2016

ObjectivesMaternal posttraumatic stress disorder (PTSD) is a risk factor for negative child adjustment, but it is unclear whether this association is direct (e.g., a mother's PTSD symptoms are observed, learned, and internalized by children which results in behavioral and emotional problems) or indirect, through parent–child relationship difficulties or parenting stress. We hypothesized that parenting stress and maternal emotional availability would exhibit indirect effects on relationships between maternal PTSD and children's functioning.MethodParticipants were 52 trauma‐exposed mothers and their children (aged 7–12 years). Mothers completed measures of PTSD and parenting stress and reported on their children's functioning. Emotional availability was assessed through observer‐rated mother–child interactions.ResultsEmotional availability was not related to PTSD or child outcomes. Parenting stress had a substantial indirect effect on the relationships between maternal PTSD and child emotion regulation, internalizing, and externalizing behaviors.ConclusionsResults highlight the need to target parenting stress in interventions with trauma‐exposed families.
Changes in nail keratin observed by Raman spectroscopy after Nd:YAG laser treatment
Authors: Shin Min Kyung , Kim Tae In , Kim Wan Sun , Park Hun‐Kuk , Kim Kyung Sook 
Published: August 2016

AbstractLasers and photodynamic therapy have been considered a convergence treatment for onychomycosis, which is a fungal infection on the nail bed and nail plate. Laser therapies have shown satisfactory results without significant complications for onychomycosis; however, the mechanism of clearing remains unknown. In this work, we investigated changes in the chemical structure of nail keratin induced by Nd:YAG laser using Raman spectroscopy. Toe nails with onychomycosis were treated with 1064 nm Nd:YAG laser. After laser treatment, the disulfide band (490–590 cm−1) of nail keratin was rarely observed or was reduced in intensity. The amide I band (1500–1700 cm−1) also showed changes induced by the laser. The α‐helical (1652 cm−1) structures dominated the β‐sheet (1673 cm−1) in nontreated nail, but the opposite phenomenon was observed after laser treatment.
Molecular Dynamics of Poly(ethylene‐2,5‐furanoate) (PEF) as a Function of the Degree of Crystallinity by Dielectric Spectroscopy and Calorimetry
Authors: Dimitriadis Theodoros , Bikiaris Dimitrios N. , Papageorgiou George Z. , Floudas George 
Published: August 2016

The segmental and local dynamics of the bio‐based polyester poly(ethylene‐2,5‐furanoate) (PEF) are investigated by dielectric spectroscopy (DS) at atmospheric pressure as a function of temperature and frequency for samples prepared with different degrees of crystallinity. Crystallization significantly alters the segmental process as this is manifested in the dielectric strength and the distribution of relaxation times. Enhanced crystallinity by the different annealing protocols increases the glass temperature of the mobile amorphous fraction. A two‐phase model is adequate in describing the dynamics associated with the β‐process within the glassy state. However, the same model fails in describing the segmental dynamics at and above the glass temperature. The combined differential scanning calorimetry and DS results provide evidence that for samples with a degree of crystallinity of ≈40%, approximately a third of segments are located within the restricted amorphous fraction.image
Phase separation of polymer mixtures driven by photochemical reactions: current status and perspectives
Authors: Tran‐Cong‐Miyata Qui , Nakanishi Hideyuki 
Published: August 2016

AbstractPhase separation of polymer mixtures induced by photo‐crosslinking and photopolymerization is summarized from the viewpoint of competing interactions in polymeric systems. First, the kinetics of photo‐crosslinking and photopolymerization are reviewed with particular emphasis on the Trommsdorff − Norrish effect in polymerization, which leads to the formation of a bimodal distribution of molecular weight at long irradiation time. The emergence of a very large molecular weight and the characteristic time for this effect to set in are utilized as a tool to control the temporal development of the resulting morphology. The shrinkage associated with the reaction and particularly its effect on the phase separation and the morphology are discussed together with the influence of the Trommsdorff − Norrish effect. Experiments on polymerization‐induced phase separation extended from binary to ternary mixtures are described where the interfacial interactions give rise to a wide variety of morphologies. Taking advantages of light, experiments using spatial and temporal modulation have been performed to control and manipulate the phase separation. These experimental results are summarized and briefly discussed in relation to the elastic deformation induced by polymerization. Finally, an overview of theoretical studies and numerical simulation of reaction‐induced phase separation is given with some comments on the complexity of the phenomena. © 2016 Society of Chemical Industry
F2 dimer: Improved intermolecular potential energy surface using ab initio calculations
Authors: Tashakor Saeedeh , Noorbala Mohammad R. , Namazian Mansoor 
Published: August 2016

AbstractA computational study on the intermolecular potential energy of 44 different orientations of F2 dimers is presented. Basis set superposition error (BSSE) corrected potential energy surface is calculated using the supermolecular approach at CCSD(T) and QCISD(T) levels of theory. The interaction energies obtained using the aug‐cc‐pVDZ and aug‐cc‐pVTZ basis sets are extrapolated to the complete basis set limit using the latest extrapolation scheme. The basis set effect is checked and it is found that the extrapolated intermolecular energies provide the best compromise between the accuracy and computational cost. Among 1320 energy points of F2–F2 system covering more relative orientations, the most stable structure of the dimers was obtained with a well depth of −146.62 cm−1 that related to cross configuration, and the most unstable structure is related to linear orientation with a well depth of −52.63 cm−1. The calculated second virial coefficients are in good agreement with experimental data. The latest extrapolation scheme of the complete basis set limit at the CCSD(T) level of theory is used to determine the intermolecular potential energy surface of the F2 dimer. Comparing the results obtained by the latest scheme with those by older schemes show that the new approach provides the best compromise between accuracy and computational cost.