bluuebunny/crossref_metadata_2025 huggingface dataset:
ChemInform Abstract: An Update on the Synthesis of β‐Lactams
Authors: Aranda M. Teresa , Perez‐Faginas Paula , Muniz Rosario Gonzalez
Published: September 2014

Review: [asymmetric synthesis of β‐lactams through [2 + 2] cycloaddition reactions; 285 refs.].
ChemInform Abstract: Olefin Metathesis by Supported Metal Oxide Catalysts
Authors: Lwin Soe , Wachs Israel E.
Published: September 2014

Review: 243 refs.
ChemInform Abstract: Studying the Dynamic Behavior of Porphyrins as Prototype Functional Molecules by Scanning Tunnelling Microscopy Close to Room Temperature
Authors: Marbach H. , Steinrueck H.‐P
Published: September 2014

Review: 116 refs.
ChemInform Abstract: Growth of Boronic Acid Based Two‐Dimensional Covalent Networks on a Metal Surface under Ultrahigh Vacuum
Authors: Clair Sylvain , Abel Mathieu , Porte Louis
Published: September 2014

Review: 79 refs.
ChemInform Abstract: Morphological, Physiological, and Biochemical Properties of Fungal Cells Located on a Liquid‐Surface and an Organic‐Aqueous Interface
Authors: Oda Shinobu
Published: September 2014

Review: 45 refs.
ChemInform Abstract: Enzymatic Hydrolysis of Biomass at High‐Solids Loadings — A Review
Authors: Modenbach Alicia A. , Nokes Sue E.
Published: September 2014

Review: 67 refs.
ChemInform Abstract: Recent Advances in Zinc—Air Batteries
Authors: Li Yanguang , Dai Hongjie
Published: September 2014

Review: 214 refs.
ChemInform Abstract: Synthesis and Applications of Hierarchically Porous Catalysts
Authors: Li Xiaoyun , Sun Minghui , Rooke Joanna Claire , Chen Lihua , Su Baolian
Published: September 2014

Review: 315 refs.
ChemInform Abstract: Surface Chemistry Dependence of Water Adsorption on Solid Substrates in Humid Ambient and Humidity Effects on Wear of Copper and Glass Surfaces
Authors: Barthel A. J. , Kim S. H.
Published: September 2014

Review: 23 refs.
ChemInform Abstract: Mesosilica Materials and Organic Pollutant Adsorption: Part B Removal from Aqueous Solution
Authors: Gibson L. T.
Published: September 2014

Review: 45 refs.
ChemInform Abstract: A New Scenario for Green & Sustainable Chemical Production
Authors: Perathoner Siglinda , Centi Gabriele
Published: September 2014

Review: 59 refs.
ChemInform Abstract: Toward a More Complete Understanding of Noncovalent Interactions Involving Aromatic Rings
Authors: Wheeler Steven E. , Bloom Jacob W. G.
Published: September 2014

Review: 147 refs.
ChemInform Abstract: Application of Electronic Circular Dichroism in the Study of Supramolecular Systems
Authors: Pescitelli Gennaro , Di Bari Lorenzo , Berova Nina
Published: September 2014

Review: 50 refs.
ChemInform Abstract: Introduction to Biological Solid‐State NMR
Authors: Weingarth M. , Baldus M.
Published: September 2014

Review: [50 refs.
ChemInform Abstract: Location Change Method for Imaging Chemical Reactivity and Catalysis with Single‐Molecule and ‐Particle Fluorescence Microscopy
Authors: Blum S. A.
Published: September 2014

Review: 31 refs.
In Situ EPR Spectroscopy in Heterogeneous Catalysis: Stepchild or Ray of Hope?
Authors: Brückner Angelika
Published: September 2014

In diesem Übersichtsartikel wird das Potenzial der Elektronenspinresonanz‐Spektroskopie (ESR, electron paramagnetic resonance, EPR) als In‐situ‐Methode für Untersuchungen von Struktur‐Reaktivitäts‐Beziehungen in der heterogenen Katalyse analysiert. Nach einer kurzen Einführung zum Stand der Technik auf diesem Gebiet sowie in die theoretischen Grundlagen der Methode werden typische Anwendungsmöglichkeiten anhand von drei praktischen Beispielen illustriert. Am Schluss steht eine kritische Bewertung von Möglichkeiten und Grenzen der Methode in der heterogenen Katalyse.
Efficiency of Carbohydrate Additives on the Stability of Horseradish Peroxidase (HRP): HRP‐Catalyzed Removal of Phenol and Malachite Green Decolorization from Wastewater
Authors: Kalaiarasan Ellappan , Palvannan Thayumanavan
Published: September 2014

The present study was undertaken to develop a cost effective stabilized horseradish peroxidase (HRP) for removal of phenol and decolorization of malachite green from synthetic wastewater. As revealed by enzyme stabilization assays, guar gum and galactose improved the stability of HRP successfully in solution state as compared as other additives such as pectin, carrageenan, or starch, respectively. In order to enhance the stability of HRP, combination of galactose and guar gum were effectively optimized together along with pH by constructing an appropriate response surface methodology (RSM). The RSM results suggest 18.25% of galactose and 0.35% of guar gum for maximum stabilization of HRP at 60°C, pH 7.4. In this study, optimization of removal of phenol and decolorization of malachite green using stabilized HRP was successfully carried out. Various process parameters such as aqueous phase of pH (7.4), concentration of enzyme (1.8 U/mL), phenol concentration (0.1 mM), and reaction time of 180 min were optimized effectively to achieve maximum removal of phenol from synthetic waste water. Dye decolorization studies indicated that stabilized HRP (1.2 U/mL) required lower concentration than the native enzyme (2 U/mL) to obtain similar decolorization efficiency. In addition, stabilized enzyme successfully decolorized the dye at 60°C, pH 7.2.
Synthesis of a Carbon Molecular Sieve from Broom Corn Stalk via Carbon Deposition of Methane for the Selective Separation of a CO2/CH4 Mixture
Authors: Banisheykholeslami Fatemeh , Ghoreyshi Ali Asghar , Mohammadi Maedeh , Pirzadeh Kasra
Published: September 2014

A carbon molecular sieve (CMS) was prepared from broom corn stalk as a low cost precursor by carbon vapor deposition of methane. The base activated carbon (AC) was produced from the broom corn stalk using ZnCl2 as the chemical activating agent. To produce the CMS, the pore structure of the AC prepared at the optimized condition was modified by chemical vapor deposition of methane. The CO2 and CH4 adsorption capacity of the developed CMS and the base AC was experimentally measured using the volumetric technique in the temperature range of 288–308 K and a pressure range of 1–40 bar. Experimental data revealed a better CO2/CH4 separation selectivity for the CMS compared to the AC. The results demonstrated the successful deposition of carbon on the AC during chemical vapor deposition of methane, where the Brunauer–Emmett–Teller surface area decreased from 1121 to 815 m2 g−1 and the micropores showed a reduced volume from 0.57 to 0.30 cm3 g−1. The enhancement of ideal selectivity from 3.5 for the base AC to 26.0 for the CMS was attributed to the molecular sieving effect due to the reduction of the average pore diameter from 2.02 to 1.47 nm. The evaluation of the isosteric heat of adsorption demonstrated the exothermic nature of the gas adsorption onto the synthesized CMS.
Drug Screening Boosted by Hyperpolarized Long‐Lived States in NMR
Authors: Buratto Roberto , Bornet Aurélien , Milani Jonas , Mammoli Daniele , Vuichoud Basile , Salvi Nicola , Singh Maninder , Laguerre Aurélien , Passemard Solène , Gerber‐Lemaire Sandrine , Jannin Sami , Bodenhausen Geoffrey
Published: September 2014

Transverse and longitudinal relaxation times (T1ρ and T1) have been widely exploited in NMR to probe the binding of ligands and putative drugs to target proteins. We have shown recently that long‐lived states (LLS) can be more sensitive to ligand binding. LLS can be excited if the ligand comprises at least two coupled spins. Herein we broaden the scope of ligand screening by LLS to arbitrary ligands by covalent attachment of a functional group, which comprises a pair of coupled protons that are isolated from neighboring magnetic nuclei. The resulting functionalized ligands have longitudinal relaxation times T1(1H) that are sufficiently long to allow the powerful combination of LLS with dissolution dynamic nuclear polarization (D‐DNP). Hyperpolarized weak “spy ligands” can be displaced by high‐affinity competitors. Hyperpolarized LLS allow one to decrease both protein and ligand concentrations to micromolar levels and to significantly increase sample throughput.
Dying in cancer centers: Do the circumstances allow for a dignified death?
Authors: Jors Karin , Adami Sandra , Xander Carola , Meffert Cornelia , Gaertner Jan , Bardenheuer Hubert , Buchheidt Dieter , Mayer‐Steinacker Regine , Viehrig Marén , George Wolfang , Becker Gerhild
Published: September 2014

BACKGROUND

Prior research has shown that hospitals are often ill‐prepared to provide care for dying patients. This study assessed whether the circumstances for dying on cancer center wards allow for a dignified death.

METHODS

In this cross‐sectional study, the authors surveyed physicians and nurses in 16 hospitals belonging to 10 cancer centers in Baden‐Wuerttemberg, Germany. A revised questionnaire from a previous study was used, addressing the following topics regarding end‐of‐life care: structural conditions (ie, rooms, staff), education/training, working environment, family/caregivers, medical treatment, communication with patients, and dignified death.

RESULTS

In total, 1131 surveys (response rate = 50%) were returned. Half of the participants indicated that they rarely have enough time to care for dying patients, and 55% found the rooms available for dying patients unsatisfactory. Only 19% of respondents felt that they had been well‐prepared to care for the dying (physicians = 6%). Palliative care staff reported much better conditions for the dying than staff from other wards (95% of palliative care staff indicated that patients die in dignity on their ward). Generally, physicians perceived the circumstances much more positively than nurses, especially regarding communication and life‐prolonging measures. Overall, 57% of respondents believed that patients could die with dignity on their ward.

CONCLUSIONS

Only about half of the respondents perceived that a dignified death is possible on their ward. We recommend that cancer centers invest more in staffing, adequate rooms for dying patients, training in end‐of‐life care, advance‐care planning standards, and the early integration of specialist palliative care services. Cancer 2014;120:3254–3260. © 2014 American Cancer Society.
Quantitative analysis of afferents expressing substance P, calcitonin gene‐related peptide, isolectin B4, neurofilament 200, and Peripherin in the sensory root of the rat trigeminal ganglion
Authors: Bae Jin Young , Kim Jae Hyun , Cho Yi Sul , Mah Won , Bae Yong Chul
Published: September 2014

Substance P (SP), calcitonin gene‐related peptide (CGRP), and isolectin B4 (IB4) are widely used as markers for peripheral neurons with unmyelinated fibers, whereas neurofilament 200 (NF200), and Peripherin are used as markers for neurons with myelinated fibers, and with unmyelinated or small‐caliber fibers, respectively. To study the selectivity of these markers for specific neuronal types, we analyzed their expression in neurons in the rat trigeminal ganglion by light‐ and electron‐microscopic immunocytochemistry. Most SP‐immunopositive (+), CGRP+, and IB4+ fibers were unmyelinated, but a small fraction (∼5%) were small myelinated fibers (<20 µm2 in cross‐sectional area, equivalent to <5 µm in diameter, Aδ fiber). Similarly, whereas the majority of NF200+ fibers were myelinated, a large fraction (23.9%) were unmyelinated, and whereas the majority of Peripherin+ fibers were unmyelinated and small myelinated, a significant fraction (15.5%) were large myelinated (>20 µm2 in cross‐sectional area, equivalent to >5 µm in diameter, Aβ fiber). Our findings confirm that SP, CGRP, and IB4 can be used as reliable markers for neurons with unmyelinated fibers, and question the suitability of NF200 as a marker for neurons with myelinated fibers, and of Peripherin as a marker for neurons with unmyelinated, or fine‐caliber fibers. J. Comp. Neurol. 523:126–138, 2015. © 2014 Wiley Periodicals, Inc.
Morphology and connectivity of parabrachial and cortical inputs to gustatory thalamus in rats
Authors: Holtz Stephen L. , Fu Anqi , Loflin Wyatt , Corson James A. , Erisir Alev
Published: September 2014

The ventroposterior medialis parvocellularis (VPMpc) nucleus of the thalamus, the thalamic relay nucleus for gustatory sensation, receives primary input from the parabrachial nucleus, and projects to the insular cortex. To reveal the unique properties of the gustatory thalamus in comparison with archetypical sensory relay nuclei, this study examines the morphology of synaptic circuitry in the VPMpc, focusing on parabrachiothalamic driver input and corticothalamic feedback. Anterogradely visualized parabrachiothalamic fibers in the VPMpc bear large swellings. At electron microscope resolution, parabrachiothalamic axons are myelinated and make large boutons, forming multiple asymmetric, adherent, and perforated synapses onto large‐caliber dendrites and dendrite initial segments. Labeled boutons contain dense‐core vesicles, and they resemble a population of terminals within the VPMpc containing calcitonin gene‐related peptide. As is typical of primary inputs to other thalamic nuclei, parabrachiothalamic terminals are over five times larger than other inputs, while constituting only 2% of all synapses. Glomeruli and triadic arrangements, characteristic features of other sensory thalamic nuclei, are not encountered. As revealed by anterograde tracer injections into the insular cortex, corticothalamic projections in the VPMpc form a dense network of fine fibers bearing small boutons. Corticothalamic terminals within the VPMpc were also observed to synapse on cells that were retrogradely filled from the same injections. The results constitute an initial survey describing unique anatomical properties of the rodent gustatory thalamus. J. Comp. Neurol. 523:139–161, 2015. © 2014 Wiley Periodicals, Inc.
Transcriptomic Studies on Liver Toxicity of Acetaminophen
Authors: Toska Endrit , Zagorsky Robert , Figler Bryan , Cheng Feng
Published: September 2014

Preclinical Research

Acetaminophen is widely used as a pain reliever and to reduce fever. At high doses, it can cause severe hepatotoxicity. Acetaminophen overdose has become the leading cause of acute liver failure in the US. The mechanisms for acetaminophen‐induced liver injury are unclear. Transcriptomic studies can identify the changes in expression of thousands of genes when exposed to supratherapeutic doses of acetaminophen. These studies elucidated the mechanism of acetaminophen‐induced hepatotoxicity and also provide insight into future development of diagnosis and treatment options for acetaminophen‐induced acute liver failure. The following is a brief overview of some recent transcriptomic studies and gene‐expression‐based prediction models on liver toxicity induced by acetaminophen.
Short‐term intensive insulin therapy at diagnosis in type 2 diabetes: plan for filling the gaps
Authors: Weng Jianping , Retnakaran Ravi , Ariachery C Ammini , Ji Linong , Meneghini Luigi , Yang Wenying , Woo Jeong‐Taek
Published: September 2014

Short‐term intensive insulin therapy is unique amongst therapies for type 2 diabetes because it offers the potential to preserve and improve beta‐cell function without additional pharmacological treatment. On the basis of clinical experience and the promising results of a series of studies in newly diagnosed patients, mostly in Asian populations, an expert workshop was convened to assess the available evidence and the potential application of short‐term intensive insulin therapy should it be advocated for inclusion in clinical practice. Participants included primary care physicians and endocrinologists. We endorse the concept of short‐term intensive insulin therapy as an option for some patients with type 2 diabetes at the time of diagnosis and have identified the following six areas where additional knowledge could help clarify optimal use in clinical practice: (1) generalizability to primary care, (2) target population and biomarkers, (3) follow‐up treatment, (4) education of patients and providers, (5) relevance of ethnicity, and (6) health economics. © 2014 The Authors. Diabetes Metabolism Research and Reviews published by John Wiley & Sons, Ltd.
Reasoning and Dyslexia: is Visual Memory a Compensatory Resource?
Authors: Bacon Alison M. , Handley Simon J.
Published: September 2014

Effective reasoning is fundamental to problem solving and achievement in education and employment. Protocol studies have previously suggested that people with dyslexia use reasoning strategies based on visual mental representations, whereas non‐dyslexics use abstract verbal strategies. This research presents converging evidence from experimental and individual differences perspectives. In Experiment 1, dyslexic and non‐dyslexic participants were similarly accurate on reasoning problems, but scores on a measure of visual memory ability only predicted reasoning accuracy for dyslexics. In Experiment 2, a secondary task loaded visual memory resources during concurrent reasoning. Dyslexics were significantly less accurate when reasoning under conditions of high memory load and showed reduced ability to subsequently recall the visual stimuli, suggesting that the memory and reasoning tasks were competing for the same visual cognitive resource. The results are consistent with an explanation based on limitations in the verbal and executive components of working memory in dyslexia and the use of compensatory visual strategies for reasoning. There are implications for cognitive activities that do not readily support visual thinking, whether in education, employment or less formal everyday settings. Copyright © 2014 John Wiley & Sons, Ltd.
Species‐specific differences in relative eye size are related to patterns of edge avoidance in an Amazonian rainforest bird community
Authors: Martínez‐Ortega Cristina , Santos Eduardo S.A. , Gil Diego
Published: September 2014

Eye size shows a large degree of variation among species, even after correcting for body size. In birds, relatively larger eyes have been linked to predation risk, capture of mobile prey, and nocturnal habits. Relatively larger eyes enhance visual acuity and also allow birds to forage and communicate in low‐light situations. Complex habitats such as tropical rain forests provide a mosaic of diverse lighting conditions, including differences among forest strata and at different distances from the forest edge. We examined in an Amazonian forest bird community whether microhabitat occupancy (defined by edge avoidance and forest stratum) was a predictor of relative eye size. We found that relative eye size increased with edge avoidance, but did not differ according to forest stratum. Nevertheless, the relationship between edge avoidance and relative eye size showed a nonsignificant positive trend for species that inhabit lower forest strata. Our analysis shows that birds that avoid forest edges have larger eyes than those living in lighter parts. We expect that this adaptation may allow birds to increase their active daily period in dim areas of the forest. The pattern that we found raises the question of what factors may limit the evolution of large eyes.
Ca2+/calmodulin‐dependent protein kinase II equally induces sarcoplasmic reticulum Ca2+ leak in human ischaemic and dilated cardiomyopathy
Authors: Fischer Thomas H. , Eiringhaus Jörg , Dybkova Nataliya , Förster Anna , Herting Jonas , Kleinwächter Astrid , Ljubojevic Senka , Schmitto Jan D. , Streckfuß‐Bömeke Katrin , Renner André , Gummert Jan , Hasenfuss Gerd , Maier Lars S. , Sossalla Samuel
Published: September 2014

Aims

The sarcoplasmic reticulum (SR) Ca2+ leak is an important pathomechanism in heart failure (HF). It has been suggested that Ca2+/calmodulin‐dependent protein kinase II (CaMKII) is only relevant for the induction of the SR Ca2+ leak in non‐ischaemic but not in ischaemic HF. Therefore, we investigated CaMKII and its targets as well as the functional effects of CaMKII inhibition in human ischaemic cardiomyopathy (ICM, n = 37) and dilated cardiomyopathy (DCM, n = 40).

Methods and results

Western blots showed a significantly increased expression (by 54 ± 9%) and autophosphorylation at Thr286 (by 129 ± 29%, P < 0.05 each) of CaMKII in HF compared with healthy myocardium. However, no significant difference could be detected in ICM compared with DCM as to the expression and autophosphorylation of CaMKII nor the phosphorylation of the target sites ryanodine receptor 2 (RyR2)‐S2809, RyR2‐S2815, and phospholamban‐Thr17. Isolated human cardiomyocytes (CMs) of patients with DCM and ICM showed a similar frequency of diastolic Ca2+ sparks (confocal microscopy) as well as of major arrhythmic events (Ca2+ waves, spontaneous Ca2+ transients). Despite a slightly smaller size of Ca2+ sparks in DCM (P < 0.01), the calculated SR Ca2+ leak [Ca2+ spark frequecy (CaSpF) × amplitude × width × duration] did not differ between CMs of ICM vs. DCM. Importantly, CaMKII inhibition by autocamide‐2‐related inhibitory peptide (AIP, 1 µmol/L) reduced the SR Ca2+ leak by ∼80% in both aetiologies (P < 0.05 each) and effectively decreased the ratio of arrhythmic cells (P < 0.05).

Conclusion

Functional and molecular measures of the SR Ca2+ leak are comparable in human ICM and DCM. CaMKII is equally responsible for the induction of the ‘RyR2 leakiness’ in both pathologies. Thus, CaMKII inhibition as a therapeutic measure may not be restricted to patients suffering from DCM but rather may be beneficial for the majority of HF patients.
Impaired NK‐cell education diminishes resistance to murine CMV infection
Authors: Wei Hairong , Nash William T. , Makrigiannis Andrew P. , Brown Michael G.
Published: September 2014

Ly49G2 (G2+) NK cells mediate murine (M)CMV resistance in MHC Dk‐expressing mice. Bone marrow transplantation (BMT) studies revealed that G2+ NK cell‐mediated MCMV resistance requires Dk in both hematopoietic and nonhematopoietic cells. As a Ly49G2 ligand, Dk in both cell lineages may contribute to lysis of virus‐infected cells. Alternatively, cellular differences in self‐MHC Dk may have affected NK‐cell education, and consequently NK cell‐mediated viral clearance. We investigated the Dk‐licensing effect on BM‐derived NK cells in BMT recipients by analyzing cytokines, cytotoxicity and MCMV resistance. In BMT recipients with lineage‐restricted Dk, G2+ NK‐cell reactivity and cytotoxicity was diminished in comparison to BMT recipients with self‐MHC in all cells. Reduced G2+ NK‐mediated MCMV resistance in BMT recipients with lineage‐restricted self‐MHC indicates that licensing of G2+ NK cells is related to NK‐cell reactivity and viral control. Titrating donor BM with self‐MHC‐bearing hematopoietic cells, as well as adoptive transfer of mature G2+ NK cells into BMT recipients with self‐MHC in non‐hematopoietic cells only, enhanced NK‐cell licensing and rescued MCMV resistance. This disparate self‐MHC NK‐cell education model would suggest that inadequately licensed NK cells corresponded to inefficient viral sensing and clearance.
CD4+FoxP3+ regulatory T cells suppress fatal T helper 2 cell immunity during pulmonary fungal infection
Authors: Schulze Bianca , Piehler Daniel , Eschke Maria , von Buttlar Heiner , Köhler Gabriele , Sparwasser Tim , Alber Gottfried
Published: September 2014

The opportunistic fungal pathogen Cryptococcus neoformans causes lung inflammation and fatal meningitis in immunocompromised patients. Regulatory T (Treg) cells play an important role in controlling immunity and homeostasis. However, their functional role during fungal infection is largely unknown. In this study, we investigated the role of Treg cells during experimental murine pulmonary C. neoformans infection. We show that the number of CD4+FoxP3+ Treg cells in the lung increases significantly within the first 4 weeks after intranasal infection of BALB/c wild‐type mice. To define the function of Treg cells we used DEREG mice allowing selective depletion of CD4+FoxP3+ Treg cells by application of diphtheria toxin. In Treg cell‐depleted mice, stronger pulmonary allergic inflammation with enhanced mucus production and pronounced eosinophilia, increased IgE production, and elevated fungal lung burden were found. This was accompanied by higher frequencies of GATA‐3+ T helper (Th) 2 cells with elevated capacity to produce interleukin (IL)‐4, IL‐5, and IL‐13. In contrast, only a mild increase in the Th1‐associated immune response unrelated to the fungal infection was observed. In conclusion, the data demonstrate that during fungal infection pulmonary Treg cells are induced and preferentially suppress Th2 cells thereby mediating enhanced fungal control.
Modelling the Luminescence of Phosphonate Lanthanide–Organic Frameworks
Authors: Nolasco Mariela M. , Mendes Ricardo F. , Lima Patrícia P. , Almeida Paz Filipe A. , Carlos Luís D. , Rocha João
Published: September 2014

The suitability of the computer package LUMPAC to calculate the photoluminescence properties of metal–organic frameworks was assessed by considering three systems based on the ditopic 1,4‐phenylenebis(methylene)diphosphonic acid (H4pmd) ligand and Ln3+ ions, namely, [Eu(Hpmd)(H2O)] (1), [La2(H2pmd)(pmd)(H2O)2] (2) and [La2(H2pmd)3(H2O)12] (3, previously reported) and their isotypical materials doped with Eu3+ cations, [(La0.95Eu0.05)2(H2pmd)(pmd)(H2O)2] (4) and [(La0.95Eu0.05)2(H2pmd)3(H2O)12] (5). These materials were prepared, and their structures and luminescence properties were characterized. A straightforward approximation based on the simple crystallographic structural subunits of these materials was used and resulted in an excellent agreement between the calculated and experimental properties. The intramolecular energy transfer and back‐transfer rates were predicted, and the T1 → 5D1 channel was shown to be the dominant pathway (9.03 × 104 s–1 for 1, 1.06 × 104 s–1 for 4 and 2.18 × 105 s–1 for 5).
Reactions of Bis(dibenzobarrelenyl) Dichalcogenides with a Palladium(0) Complex: Unexpected Formations of Mononuclear Chalcogenide(dichalcogenolato)palladium(II) Complexes and Dichalco­genahexacyclo Compounds
Authors: Nakata Norio , Yamaguchi Yuki , Ishii Akihiko
Published: September 2014

Thermal reactions of bis(dibenzobarrelenyl) dichalcogenides [(DbbS)2 and (DbbSe)2] with [Pd(PPh3)4] in toluene afforded novel mononuclear chalcogenide(dichalcogenolato)PdII complexes [Pd(EDbb‐12‐EDbb)(EDbb)(PPh3)] (E = S, Se) together with dichalcogenahexacyclo compounds. The reaction in the presence of PPh3 in toluene at 110 °C led to a cyclometalation to furnish the corresponding four‐membered 1,2‐chalcogenapalladacycles [Pd(EDbb)(PPh3)2] (E = S, Se) with dichalcogenahexacyclo compounds. The structures of these PdII complexes and cyclization products were fully characterized on the basis of their NMR spectroscopic data and X‐ray analyses. In the crystalline state of [Pd(SDbb‐12‐SDbb)(SDbb)(PPh3)], two thiolato sulfur atoms occupy cis positions with respect to the PPh3, and the sulfide sulfur atom from the chelating sulfido(thiolato) ligand is situated at the trans position.
Water‐Soluble Heteronuclear [NaCuII6] Metallomacrocyclic Sandwich Complexes: Synthesis, Structure, Properties and In Vitro Biological Studies
Authors: Patra Ayan , Saha Santu Kumar , Sen Tamal K. , Carrella Luca , Musie Ghezai T. , Khuda‐Bukhsh Anisur Rahman , Bera Manindranath
Published: September 2014

The water‐soluble heteronuclear metallomacrocyclic sandwich clusters [NaCu6(hpnbpda)3(OH)3(OH2)3](NO3)·4H2O (1), [NaCu6(hpnbpda)3(OH)3(OH2)3](ClO4) (2), and [NaCu6(hpnbpda)3(OH)3(OH2)3](PF6) (3) [H3hpnbpda = N,N′‐bis(2‐pyridylmethyl)‐2‐hydroxy‐1,3‐propanediamine‐N,N′‐diacetic acid] have been synthesized in methanol at room temperature and fully characterized using several analytical techniques including single‐crystal X‐ray diffraction. The molecular architecture of complex 1 is built from the template assembly of three dinuclear [Cu2(hpnbpda)]+ fragments through their weak oxophillic interactions with a central sodium(I) cation. A close analysis of the single‐crystal X‐ray structure reveals that the metallic core of cluster 1 consists of six highly distorted octahedral CuII ions arranged at the corners of a trigonal prism that encapsulates the sodium(I) ion. Complex 1 displays a rare μ3:η2:η1:η1 bridging mode of six carboxylate groups of three hpnbpda3– ligands with each bridging between two copper(II) atoms and the sodium(I) center. Variable‐temperature magnetic‐susceptibility measurements (2–300 K) on a powdered microcrystalline sample reveal that the paramagnetic copper centers in complex 1 are antiferromagnetically coupled to one another. Systematic biological investigation such as cytotoxicity assessment, DNA content analysis in terms of cell‐cycle distribution by means of the fluorescence‐activated cell sorting (FACS) method, DNA binding, DNA cleavage, and the underlying mechanism of possible apoptotic cell‐death events in human cervical cancer cells (HeLa) were carried out in detail using complex 1. The in vitro assays using complex 1 in HeLa cells provided new findings that indicate its possible future therapeutic application. Theoretical calculations were carried out to find the Fukui functions at the metal sites in complex 1 to predict the possible metal centers involved in the DNA binding.
Structural and Reactivity Consequences of Reducing Steric Bulk of N,N′‐Diarylformamidinates Coordinated to Lanthanoid Ions
Authors: Deacon Glen B. , Junk Peter C. , Macreadie Lauren K. , Werner Daniel
Published: September 2014

Redox transmetallation/protolysis reactions between rare‐earth metals, Hg(C6F5)2, and N,N′‐bis(4‐methylphenyl)formamidine (p‐TolFormH) in THF initially produce a THF solvated species [Ln(p‐TolForm)3(thf)2] (Ln = La, Ce, Nd, Sm). Upon addition of non‐coordinating solvents, coordinated THF is rapidly liberated, producing unsolvated, dimeric complexes of the general formula [Ln(p‐TolForm)3]2 [Ln = La (La1), Ce (Ce2), Nd (Nd3a), Sm (Sm4a)], containing rare μ‐1κ(N,N′):2κ(N,N′) formamidinate ligands bridging between the two metal centres. Such binding is unprecedented in rare‐earth N,N′‐diarylformamidinate chemistry, and is generally uncommon in formamidinate or amidinate coordination chemistry. This tendency for THF liberation is metal size dependent since the smaller lutetium analogue [Lu(p‐TolForm)3(thf)] (Lu5) remains solvated with a seven coordinate monomeric structure. The dimeric species Sm4a is cleaved by treatment with Ph3PO, N,N′‐bis(2,6‐difluorophenyl)formamidine (DFFormH), or [K(p‐TolForm)(18‐Crown‐6)] producing [Sm(p‐TolForm)3(Ph3PO)2] (Sm4b), [Sm(DFForm)2(p‐TolForm)(thf)2] (Sm4c), and the charge separated [K(18‐Crown‐6)][Sm(p‐TolForm)4] (Sm4e) respectively, the last being the first complex with a discrete [Ln(ArForm)4]– ion.
Preparation of Cyclohexenones from Acyclic (Pentadienyl)iron(1+) Cations: Synthetic Studies Directed toward the A‐Ring of Dihydrotachysterols
Authors: Manful Charles F. , Donaldson William A.
Published: September 2014

The reaction of tricarbonyl(3‐methylpentadienyl)iron(1+) cation (7) with stabilized carbon nucleophiles affords 4‐methyl‐5‐substituted cyclohexenones. Reaction of 7 with sodium bis[(+)‐2‐phenylcyclohexyl]malonate afforded a mixture of diastereomers (de = 60 %); the diastereomeric allylic alcohols resulting from Luche reduction of this mixture were separable by column chromatography. Issues in diastereoselectivity in approaches to synthons for the A‐ring of the tachysterols from these cyclohexenones are reported.
Convenient Formation of Triarylphosphines by Nickel‐Catalyzed C–P Cross‐Coupling with Aryl Chlorides
Authors: Sun Meng , Zang Yu‐Shi , Hou Le‐Kai , Chen Xiang‐Xiang , Sun Wei , Yang Shang‐Dong
Published: September 2014

A convenient strategy has been developed for the preparation of various phosphine ligands in good to excellent yields through a nickel‐catalyzed C–P bond‐forming step. This reaction proceeded smoothly and tolerated a variety of functional groups to provide a new method for the synthesis of important phosphine ligands through the direct cleavage of a C–Cl bond.
Venerupis decussata under environmentally relevant lead concentrations: Bioconcentration, tolerance, and biochemical alterations
Authors: Freitas Rosa , Martins Roberto , Antunes Sara , Velez Cátia , Moreira Anthony , Cardoso Paulo , Pires Adília , Soares Amadeu M.V.M , Figueira Etelvina
Published: September 2014

The edible clam Venerupis decussata is widely distributed in European aquatic systems, some of which are under strong anthropogenic pressure, which can contribute to trophic transfer of xenobiotics to humans. Accordingly, the present study focused on the tolerance, bioconcentration, and biochemical responses of V. decussata after exposure to ecologically relevant concentrations of lead. Health risks to humans after consumption of clams was also explored. An acute toxicity assay (96 h) was conducted with wild clams, using Pb exposure concentrations ranging from 0 mg L−1 to 1.80 mg L−1. Lethality, bioconcentration factor (BCF), intracellular partitioning, and a relevant set of biomarkers were used as endpoints. Clams, interstitial water, water column, and sediment samples were collected to analyze Pb concentration. The Pb concentration in wild clams was below international consumption guidelines. Under laboratory conditions, clams revealed high sensitivity to Pb (median lethal concentration of 0.65 mg L−1), with a high bioconcentration ability (bioconcentration factor > 1) during exposure. The intracellular partitioning data showed that most of the Pb had accumulated in the insoluble fraction (>80%). Several significant biochemical changes were observed, namely on catalase and glutathione-S-tranferase activities and metalothionein content. Overall, it was demonstrated that the European clam has a reduced tolerance to Pb, compared with other bivalves. However, consumption of clams from the Ria de Aveiro lagoon (Portugal) does not raise public health concerns in terms of Pb. Environ Toxicol Chem 2014;33:2786–2794. © 2014 SETAC
Effect of particle and fiber size on the morphology of deposits in fibrous filters
Authors: Przekop Rafał , Gradoń Leon
Published: September 2014

The capture of aerosol particles during their production and purification of air at workplace and atmospheric environment require an efficient separation method of particulate matter from the carrier gas. Many papers have been published recently on the deposition of particles on fibrous collectors, often using the classical continuum approach to describe the process. However, the approach is not convenient for studying the influence of particle deposition on filter performance (filtration efficiency and pressure drop) when one has to introduce nonsteady‐state boundary conditions. For the purpose of this work, the lattice Boltzmann model describes fluid dynamics, while the solid particle motion is modeled by the Brownian dynamics. The aim of this study is to model the influence of single particle loading (amount and morphology – e.g., porosity and fractal dimension) on its performance. Copyright © 2014 John Wiley & Sons, Ltd.
Novel bioresorbable stent coating for drug release in congenital heart disease applications
Authors: Goodfriend Amy C. , Welch Tré R. , Barker Greg , Ginther Richard , Riegel Matthew S. , Reddy Surendranath Veeram , Wang Jian , Nugent Alan , Forbess Joseph
Published: September 2014

A novel double opposed helical poly‐l‐lactic acid (PLLA) bioresorbable stent has been designed for use in pediatrics. The aim was to test the PLLA stent biocompatibility. The PLLA stent was immersed into whole pig's blood in a closed loop circuit then fibrin and platelet association was assessed via enzyme‐linked immunosorbent assay. D‐Dimer was valued at 0.2 ± 0.002 ng/mL and P‐selectin 0.43 ± 00.01 ng/mL indicating limited association of fibrin and platelets on the stent. To improve biocompatibility by targeting inflammatory cells, dexamethasone was incorporated on PLLA fibers with two coating methods. Both coatings were poly(l‐lactide‐co‐glycolide) acid (PLGA) but one was made porous with sucrose while the other remained nonporous. There was no change in mechanical properties of the fiber with either coating of PLGA polymer. The total amount of dexamethasone released was then determined for each coating. The cumulative drug release for the porous fiber was significantly higher (∼100%) over 8 weeks than the nonporous fiber (40%). Surface examination of the fiber with scanning electron microscopy showed more surface microfracturing in coatings that contain pores. The biocompatibility of this novel stent was demonstrated. Mechanical properties of the fiber were not altered by coating with PLGA polymer. Anti‐inflammatory drug release was optimized using a porous PLGA polymer. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 103A: 1761–1770, 2015.
Influence of Nuclear Blebs and Micronuclei Status on the Growth Kinetics of Human Mesenchymal Stem Cells
Authors: Sharma Shikha , Bhonde Ramesh
Published: September 2014

Therapeutic potential of mesenchymal stem cells (MSCs) demands assurance of the quality, safety, and genetic stability. Nuclear blebs (NBs) and Micronuclei (MNs) are considered as biomarkers for cancer and an increase in their numbers is associated with malignancy and other pathologic disorders. However, the status of NBs and MNs in MSCs is not known. Hence we examined the frequency of NBs and MNs in MSCs from umbilical cord (UC‐MSCs) and placenta (PD‐MSCs) and found a difference in the number of NBs and MNs depending on the source of the MSCs. The number of NBs and MNs was always found to be less in UC‐MSCs as compared to PD‐MSCs obtained from the same patient. Furthermore, we observed that the number of NBs was inversely proportional to the proliferation rate of the cells. The cryopreservation of these MSCs over 6 months also led to increase in the number of NBs and MNs thus slowing down their rate of proliferation on revival. MSCs from both the sources exhibiting high NBs and MNs showed longer S phase and G2‐M arrest and increase in senescent cells without altering their CD‐marker profile and differentiation potential. This feature was consistent with the upregulation of cell cycle checkpoint genes (p53, p21, Gadd45, ATM, ATR, chek2, p27, p16, and p10). In conclusion, our data demonstrates for the first time the importance of checking the occurrence of NBs and MNs in MSCs before using them for cellular therapy as a quality control measure to check their genetic stability. J. Cell. Physiol. 230: 657–666, 2015. © 2014 Wiley Periodicals, Inc., A Wiley Company
Effect of CYP2C9–VKORC1 interaction on warfarin stable dosage and its predictive algorithm
Authors: Li Xi , Liu Rong , Yan Han , Tang Jie , Yin Ji‐Ye , Mao Xiao‐Yuan , Yang Fang , Luo Zhi‐Yin , Tan Sheng‐Lan , He Hui , Chen Xiao‐Ping , Liu Zhao‐Qian , Li Zhi , Zhou Hong‐Hao , Zhang Wei
Published: September 2014

This study aimed to identify the effect of CYP2C9–VKORC1 interaction on warfarin dosage requirement and its predictive algorithm by investigating four populations. Generalized linear model was used to evaluate the relationship between the interaction and warfarin stable dosage (WSD), whereas multiple linear regression analysis was applied to construct the WSD predictive algorithm. To evaluate the effect of CYP2C9–VKORC1 interaction on the predictive algorithms, we compared the algorithms with and without the interaction. The interaction was significantly associated with WSD in the Chinese and White cohorts (P values < 0.05). In the algorithms that considered the interaction, the predictive success rates improved by only 0.12% in the Chinese patients and by a maximum of 0.02% in the White patients under four different CYP2C9 classifications. Thus, VKORC1–CYP2C9 interaction can affect WSD. However, the discrepancy between the predictive results obtained using the predictive algorithm with and without CYP2C9–VKORC1 interaction was negligible and can therefore be disregarded.
3‐bromopyruvate inhibits glycolysis, depletes cellular glutathione, and compromises the viability of cultured primary rat astrocytes
Authors: Ehrke Eric , Arend Christian , Dringen Ralf
Published: September 2014

The pyruvate analogue 3‐bromopyruvate (3‐BP) is an electrophilic alkylator that is considered a promising anticancer drug because it has been shown to kill cancer cells efficiently while having little toxic effect on nontumor cells. To test for potential adverse effects of 3‐BP on brain cells, we exposed cultured primary rat astrocytes to 3‐BP and investigated the effects of this compound on cell viability, glucose metabolism, and glutathione (GSH) content. The presence of 3‐BP severely compromised cell viability and slowed cellular glucose consumption and lactate production in a time‐ and concentration‐dependent manner, with half‐maximal effects observed at about 100 µM 3‐BP after 4 hr of incubation. The cellular hexokinase activity was not affected in 3‐BP‐treated astrocytes, whereas within 30 min after application of 3‐BP the activity of glyceraldehyde‐3‐phosphate dehydrogenase (GAPDH) was inhibited, and cellular GSH content was depleted in a concentration‐dependent manner, with half‐maximal effects observed at about 30 µM 3‐BP. The depletion of cellular GSH after exposure to 100 µM 3‐BP was not prevented by the presence of 10 mM of the monocarboxylates lactate or pyruvate, suggesting that 3‐BP is not taken up into astrocytes predominantly by monocarboxylate transporters. The data suggest that inhibition of glycolysis by inactivation of GAPDH and GSH depletion contributes to the toxicity that was observed for 3‐BP‐treated cultured astrocytes. © 2014 Wiley Periodicals, Inc.
New food from a potato somatic hybrid: nutritional equivalence and safety assessment by a feeding study on rats
Authors: Nouri‐Ellouz Oumèma , Zeghal Najiba , Makni Saloua , Makni‐Ayadi Fatma , Trigui Mouhanad , Ellouz‐Ghorbel Raoudha , Drira Noureddine , Sellami‐Boudawara Tahya , Gargouri‐Bouzid Radhia
Published: September 2014

BACKGROUND

Potato tubers from the STBd somatic hybrid line that exhibited improved tolerance to salinity and resistance to fungal and PVY infections were characterised. They were compared for their chemical composition to the Spunta variety produced by conventional agronomic practices. This study aimed to compare nutritional value and safety by feeding rats with STBd or commercial tubers added to the standard diet (20/80 w/w).

RESULTS

The analysis of soluble sugar, fat, fibre and ash content of tubers did not reveal any significant differences between the hybrid line and the control Spunta variety. Small differences were observed in dry matter, starch and protein content of hybrid potatoes in comparison to controls. However, all values were within normal ranges reported in the literature. The feeding study on rats showed that overall health, weight gain, food consumption, morphological aspects and weights of organs were comparable between rat groups fed the STBd hybrid and the Spunta variety.

CONCLUSION

Taken together, 28 days of consumption of STBd hybrid potato did not exert any adverse effect on rats compared with commercial Spunta potato. The STBd potato line was therefore considered to be as safe for food utilisation as the commercial variety. © 2014 Society of Chemical Industry
Different types of upper extremity exercise training in Duchenne muscular dystrophy: Effects on functional performance, strength, endurance, and ambulation
Authors: Alemdaroğlu Ipek , Karaduman Ayşe , Yilmaz Öznur Tunca , Topaloğlu Haluk
Published: September 2014

Introduction

We investigated and compared the effects of 2 different types of upper extremity exercise training on upper extremity function, strength, endurance, and ambulation in patients with early‐stage Duchenne muscular dystrophy (DMD).

Methods

The study group (n = 12) exercised with an arm ergometer under the supervision of a physiotherapist, whereas the control group (n = 12) underwent a strengthening range‐of‐motion (ROM) exercise program under the supervision of their families at home for 8 weeks. Upper extremity functional performance, strength, endurance, and ambulatory status were assessed before and after the training.

Results

Ambulation scores, endurance, and arm functions, as well as proximal muscle strength, were improved after the training in the study group (P < 0.05).

Conclusions

These results demonstrate that upper extremity training with an arm ergometer is more effective in preserving and improving the functional level of early‐stage DMD patients compared to ROM exercises alone. Muscle Nerve 51:697–705, 2015
The Thermochemistry of London Dispersion‐Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’
Authors: Hansen Andreas , Bannwarth Christoph , Grimme Stefan , Petrović Predrag , Werlé Christophe , Djukic Jean-Pierre
Published: September 2014

Reliable thermochemical measurements and theoretical predictions for reactions involving large transition metal complexes in which long‐range intramolecular London dispersion interactions contribute significantly to their stabilization are still a challenge, particularly for reactions in solution. As an illustrative and chemically important example, two reactions are investigated where a large dipalladium complex is quenched by bulky phosphane ligands (triphenylphosphane and tricyclohexylphosphane). Reaction enthalpies and Gibbs free energies were measured by isotherm titration calorimetry (ITC) and theoretically ‘back‐corrected’ to yield 0 K gas‐phase reaction energies (ΔE). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source of error in theoretical thermochemistry protocols. The (‘back‐corrected’) experimental reaction energies were used to benchmark (dispersion‐corrected) density functional and wave function theory methods. Particularly, we investigated whether the atom‐pairwise D3 dispersion correction is also accurate for transition metal chemistry, and how accurately recently developed local coupled‐cluster methods describe the important long‐range electron correlation contributions. Both, modern dispersion‐corrected density functions (e.g., PW6B95‐D3(BJ) or B3LYP‐NL), as well as the now possible DLPNO‐CCSD(T) calculations, are within the ‘experimental’ gas phase reference value. The remaining uncertainties of 2–3 kcal mol−1 can be essentially attributed to the solvation models. Hence, the future for accurate theoretical thermochemistry of large transition metal reactions in solution is very promising.
Anion Binding Properties of Alkynylplatinum(II) Complexes with Amide‐Functionalized Terpyridine: Host–Guest Interactions and Fluoride Ion‐Induced Deprotonation
Authors: Yeung Margaret Ching-Lam , Chu Ben Wai-Kin , Yam Vivian Wing-Wah
Published: September 2014

Molecular sensors able to detect ions are of interest due to their potential application in areas such as pollutant sequestration. Alkynylplatinum(II) terpyridine complexes with an amide‐based receptor moiety have been synthesized and characterized. Their anion binding properties based on host–guest interactions have been examined with the use of UV‐vis absorption and emission spectral titration studies. Spectral changes were observed for both complexes upon the addition of spherical and nonspherical anions. Their titration profiles were shown to be in good agreement with theoretical results predicting a 1:1 binding model, and the binding constants were determined from the experimental data. Drastic color changes from yellow to orange–red were observed for one of the complexes upon titration with fluoride (F−) ion in acetone. These changes were ascribed to the deprotonation of the amide functionalities induced by F− ion, and this was confirmed by the restoration of spectral changes upon addition of trifluoroacetic acid to the F− ion–complex mixture as well as by electrospray ionization mass spectrometry (ESI‐MS) data.