bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electronic Structures of the Electron Transfer Series [M(bpy)3]n, [M(tpy)2]n, and [Fe(tbpy)3]n (M = Fe, Ru; n = 3+, 2+, 1+, 0, 1–): A Mössbauer Spectroscopic and DFT Study
Authors: England Jason , Scarborough Christopher C. , Weyhermüller Thomas , Sproules Stephen , Wieghardt Karl 
Published: June 2012

AbstractThe five‐membered electron‐transfer series [M(bpy)3]n and [M(tpy)2]n (M = Fe, Ru; bpy = 2,2′‐bipyridine, tpy = 2,2′:6′,2″‐terpyridine) and [Fe(tbpy)3]n (tbpy = 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine; n = 3+, 2+, 1+, 0, 1–) have been investigated and the electronic structure of the so called “low‐valent” complexes (n = 1+, 0, 1–) have been established by a combination of electro‐ and magnetochemistry, electron paramagnetic resonance (EPR) and Mössbauer spectroscopy, X‐ray crystallography, and DFT calculations. These complexes are accessed by reduction of the d6 S = 0 dicationic starting materials [M(bpy)3]2+ and [M(tpy)2]2+ (M = Fe, Ru) and [Fe(tbpy)3]2+. The monocations [M(bpy·)(bpy0)2]1+ (S = 1/2) and [M(tpy·)(tpy0)]1+ (S = 1/2) (M = FeII, RuII) also contain a low‐spin (t2g)6 divalent metal center, plus a single radical monoanion (bpy·)1– or (tpy·)1–, and two or one neutral (bpy0) or (tpy0) ligands, respectively. The unpaired electron resides in a ligand π* orbital. The neutral complexes [FeII(bpy·)2(bpy0)]0 and [RuII(tpy·)2]0 were found, by DFT calculations, to possess an S = 1 ground state that is attained by weak intramolecular ferromagnetic coupling between two ligand radical anions and a singlet excited state (S = 0). In contrast, the neutral species [RuII(bpy·)2(bpy0)]0 possesses an S = 0 ground state. The metal centers of these neutral complexes retain a low‐spin (t2g)6 configuration. Remarkably, the corresponding neutral complex [FeII(tpy·)2]0 contains high‐spin FeII (SFe = 2). Strong intramolecular antiferromagnetic metal–radical coupling yields an experimentally observed S = 1 ground state. The monoanions [MII(bpy·)3]1– (M = Fe, Ru) are composed of a low‐spin metal ion [Fe, Ru; (t2g)6; SM = 0] and three (bpy·)1– radical anions.
Synthetic Methodologies for the Preparation of β‐Amino Thiols
Authors: Mercey Guillaume , Reboul Vincent , Gulea Mihaela , Levillain Jocelyne , Gaumont Annie‐Claude 
Published: June 2012

Abstractβ‐Amino thiols are an important class of bifunctional compounds that have found various applications in many areas of chemistry. This microreview highlights the synthetic methods judged to be the most efficient and general for their preparation.
Revision of the Structure and Total Synthesis of Altenuisol
Authors: Nemecek Gregor , Cudaj Judith , Podlech Joachim 
Published: June 2012

AbstractA total synthesis of the reported structure of altenuisol is described. Comparison of the 1H NMR spectra of the synthesized compound and of the natural product revealed that the originally proposed structure was not correct. Consequently, two constitutional isomers were synthesized. The spectra of one of these compounds – a structure originally proposed as the structure of altertenuol – matched perfectly with the spectra of the natural product. The total synthesis of altenuisol was thus achieved starting with phloroglucinic acid and protocatechuic aldehyde in 10 steps and in 23 % yield, where the longest linear sequence consisted of 6 steps. The key step was a Suzuki coupling with concomitant formation of the lactone ring. Whether altertenuol is identical with altenuisol could not be decided.
INCOME‐RELATED INEQUITY IN HEALTHCARE UTILISATION AMONG INDIVIDUALS WITH CARDIOVASCULAR DISEASE IN ENGLAND—ACCOUNTING FOR VERTICAL INEQUITY
Authors: Vallejo‐Torres Laura , Morris Stephen 
Published: June 2012

ABSTRACTEconomic analyses of equity which focus solely on horizontal inequity offer a partial assessment of socioeconomic inequity in healthcare use. We analyse income‐related inequity in cardiovascular disease‐related healthcare utilisation by individuals reporting cardiovascular disease in England, including both horizontal and vertical aspects. For the analysis of vertical inequity, we use target groups to estimate the appropriate relationship between healthcare needs and use. We find that including vertical inequity considerations may lead us to draw different conclusions about the nature and extent of income‐related inequity. After accounting for vertical inequity in addition to horizontal inequity, there is no longer evidence of inequity favouring the poor for nurse visits, whereas there is some evidence that doctor visits and inpatient stays are concentrated among richer individuals. The estimates of income‐related inequity for outpatient visits, electrocardiography tests and heart surgery become even more pro‐rich when accounting for vertical inequity. Copyright © 2012 John Wiley & Sons, Ltd.
Development of a support‐vector‐machine‐based model for daily pan evaporation estimation
Authors: Lin Gwo‐Fong , Lin Hsuan‐Yu , Wu Ming‐Chang 
Published: June 2012

AbstractEvaporation estimation is an important issue in water resources management. In this article, a four‐season model with optimal input combination is proposed to estimate the daily evaporation. First, the model based on support vector machine (SVM) coupled with an input determination process is used to determine the optimal combination of input variables. Second, a comparison of the SVM‐based model with the model based on back‐propagation network (BPN) is made to demonstrate the superiority of the SVM‐based model. In addition, season data are used to construct the SVM‐based four‐season model to further improve the daily evaporation estimation. An application is conducted to demonstrate the performance of the proposed model. Results show that the SVM‐based model can select the optimal input combination with physical mechanism. The SVM‐based model is more appropriate than the BPN‐based model because of its higher accuracy, robustness and efficiency. Moreover, the improvement due to the use of the four‐season model increases from 3.22% to 15.30% for RMSE and from 4.84% to 91.16% for CE, respectively. In conclusion, the SVM‐based model coupled with the proposed input determination process should be used to select input variables. The proposed four‐season SVM‐based model with optimal input combination is recommended as an alternative to the existing models. The proposed modelling technique is expected to be useful to improve the daily evaporation estimation. Copyright © 2012 John Wiley & Sons, Ltd.
Impact of cell division on intracellular uptake and nuclear targeting with fluorescent SiC‐based nanoparticles
Authors: Serdiuk Tetiana , Lysenko Vladimir , Mognetti Barbara , Skryshevsky Valery , Géloën Alain 
Published: June 2012

AbstractSemiconductor nanoparticles (NPs) became important and wide‐used tool for cell imaging because of their unique remarkable properties. Nevertheless, all previous investigations in this area were done on proliferating cells. For the first time, this work demonstrates strong influence of cell active proliferation/contact inhibition of proliferation on uptake of NPs. In addition, we show that cell division plays key‐role in penetration of silicon carbide based NPs (SiC NPs) inside the cell nucleus. This may very likely concern other types of NPs able to reach the cell nuclei. In particular, observed effect of cell division gives perspectives for future selective cancer treatment with NPs. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
A quantum chemical calculation on Fe(CO)5 revealing the operation of the Dewar–Chatt–Duncanson model
Authors: Bachler Vinzenz 
Published: June 2012

AbstractA nonstandard computational scheme has been applied to calculate Fe(CO)5 with the aim to illustrate the operation of the Dewar–Chatt–Duncanson model by computation. A full configuration interaction (CI) calculation in an active space has been performed. The active space is built from naturally localized molecular orbitals (NLMOs) localized in bond regions or forming lone pairs. For selecting this active space, Weinhold's perturbation theory formulated in the natural bond orbital (NBO) space has been applied. Bonding, lone pair, and antibond NBOs exhibiting large interaction energies serve to define the active space. The actually applied active space, however, comprises NLMOs that are close in shape to the NBOs indicated by perturbation theory. Thus, a CI calculation with localized orbitals has been performed meeting the classical reasoning of chemists that is often based on local bonding concepts. The computational scheme yields the Lewis structure for Fe(CO)5 whose energy is identical to the Hartree–Fock energy. The Lewis energy comprises CO → Fe σ‐electron transfer (ET) and CO ← Fe electron back donation (BD). This Lewis energy gets lowered by localized correlation energy contributions caused by ET processes where electrons are back donated from the Fe d‐lone pairs into the CO ligands. Thus, electron correlation within the selected active space is dominated by electron BD. Energies and electron populations of the NBOs support the notion that electrons are preferentially back donated into the equatorial CO ligands. Weights of local Slater determinants, determining the correlation energy, also point to a predominant BD into the equatorial CO ligands. Correlation energy increments resulting from electron BD into single antibond orbitals of the CO ligands have been calculated. These energy quantities also demonstrate that BD into the equatorial CO ligands is more energy lowering than BD into the axial CO ligands. © 2012 Wiley Periodicals, Inc.
Deciduous dental pulp stem cells are involved in osteoclastogenesis during physiologic root resorption
Authors: Zhu Yuan , Shang Linjuan , Chen Xiaoyan , Kong Xiangwei , Liu Na , Bai Yuyun , Fang Jun , Dang Jun , Wang Xiaojing , Jin Yan 
Published: June 2012

AbstractMultipotent mesenchymal stem cells are derived from the dental pulps of permanent teeth and exfoliated deciduous teeth, and are known to induce bone and dentin generation. However, the role of deciduous dental pulp stem cells (DDPSCs) in physiologic root resorption remains unclear. In this study, dental pulp stem cells (DPSCs) in permanent teeth (P) were retrieved and compared to DDPSCs from deciduous incisors at different root resorption stages: stable (S), middle (M), and final (F). Decalcified teeth sections showed that osteoclasts and resorption lacunae were most prevalent in the M resorption stage. DDPSC proliferation rate was also highest in the M stage. DDPSCs in the F stage produced more calcified nodules than those in the S or M stages. Alkaline phosphatase (ALP) expression was highest in the F stage, indicating that DDPSCs promote mineralization. In addition, the ratio of receptor activator of nuclear factor kappa B ligand (RANKL) and osteoprotegerin (OPG) expression was significantly higher in the M stage, indicating that DDPSCs promote resorption. Dickkopf 1 (Dkk1) expression was remarkably higher in the F and P groups, suggesting that the Wnt pathway is inhibited during the resorption process. Interestingly, despite the fact that Wnt3a down‐regulated OPG in osteogenic induction medium and up‐regulated RANKL in medium with 1,25‐dihydroxy vitamin D3 (VD3), the RANKL/OPG ratio was reduced only with VD3. Collectively, our data indicate that DDPSCs influence osteoclastogenesis during the physiologic root resorption process, and that the canonical Wnt pathway can change the RANKL/OPG expression ratio in DDPSCs. J. Cell. Physiol. 228: 207–215, 2013. © 2012 Wiley Periodicals, Inc.
Oxygen diffusivity in alginate/chitosan microcapsules
Authors: Zhao Wei , Zhang Ying , Liu Yang , Tan Mingqian , Yu Weiting , Xie Hongguo , Ma Ying , Sun Guangwei , Lv Guojun , Zhao Shan , Ma Xiaojun 
Published: June 2012

AbstractBACKGROUND: Oxygen diffusion properties affect the proliferation and metabolism of cells cultured in microcapsules with a polyelectrolyte complex membrane. The effective diffusion coefficient (De) of oxygen in alginate/chitosan (AC) microcapsules under different preparation conditions was calculated, and a mathematic model was developed to investigate the effect of oxygen diffusion on cell loading in the microcapsules.RESULTS: Oxygen De in AC microcapsules was independent of alginate solution concentration, intrinsic viscosity of alginate and different polyelectrolyte complex membranes. De decreased from 2.1 ± 0.3 × 10−9 to 0.17 ± 0.01 × 10−9 m2 s−1 as microcapsule diameter decreased from 1800 to 45 0 µm. Microcapsule density was increased from 1.013 ± 0.000 to 1.034 ± 0.003 g mL−1 as diameter decreased from 1775 to 430 µm. The mathematic model results showed that critical CHO cell loadings were 1.8 × 108 or 1.1 × 108 cells mL−1 in microcapsules with 450 or 1800 µm diameter, respectively.CONCLUSIONS: No significant difference was found of oxygen De between calcium alginate beads and AC microcapsules. The decrease of De with diameter was attributed to the increasing density and compact degree on the surface. The model results indicated that risk on necrosis rose with the increasing diameter. Microcapsules with smaller diameters may have more advantages on cell culture. © 2012 Society of Chemical Industry
Efficiency of a new strategy involving a new class of natural hetero‐ligand iron(III) chelates (Fe(III)‐NHL) to improve fruit tree growth in alkaline/calcareous soils
Authors: Fuentes Marta , Ortuño María F , Pérez‐Sarmiento Francisco , Bacaicoa Eva , Baigorri Roberto , Conejero Wenceslao , Torrecillas Arturo , García‐Mina José M 
Published: June 2012

AbstractBACKGROUND: Iron (Fe) chlorosis is a serious problem affecting the yield and quality of numerous crops and fruit trees cultivated in alkaline/calcareous soils. This paper describes the efficiency of a new class of natural hetero‐ligand Fe(III) chelates (Fe‐NHL) to provide available Fe for chlorotic lemon trees grown in alkaline/calcareous soils. These chelates involve the participation in the reaction system of a partially humified lignin‐based natural polymer and citric acid.RESULTS: First results showed that Fe‐NHL was adsorbed on the soil matrix while maintaining available Fe for plants in alkaline/calcareous solution. The effects of using three different sources as Fe fertilisers were also compared: two Fe‐NHL formulations (NHL1, containing 100% of Fe as Fe‐NHL, and NHL2, containing 80% of Fe as Fe‐NHL and 20% of Fe as Fe‐ethylenediamine‐N,N′‐bis‐(o‐hydroxyphenylacetic) acid (Fe‐EDDHA)) and Fe‐EDDHA. Both Fe‐NHL formulations increased fruit yield without negative effects on fruit quality in comparison with Fe‐EDDHA. In the absence of the Fe‐starter fraction (NHL1), trees seemed to optimise Fe assimilation and translocation from Fe‐NHL, directing it to those parts of the plant more involved in development.CONCLUSION: The field assays confirmed that Fe‐NHL‐based fertilisers are able to provide Fe to chlorotic trees, with results comparable to Fe‐EDDHA. Besides, this would imply a more sustainable and less expensive remediation than synthetic chelates. Copyright © 2012 Society of Chemical Industry
Physicochemical properties and emulsion stabilization of rice dreg glutelin conjugated with κ‐carrageenan through Maillard reaction
Authors: Du Yanxue , Shi Suhua , Jiang Yan , Xiong Hua , Woo Meng Wai , Zhao Qiang , Bai Chunqing , Zhou Qiang , Sun Wenjing 
Published: June 2012

AbstractBACKGROUND: Rice dreg is an underutilized source of cereal protein with good potential for application in the food industry. Glutelin represents about 850 g kg−1 of total storage protein in rice dreg. The objective of this study was to characterize the physicochemical properties and emulsion stabilization of the Maillard type conjugate formed with rice dreg glutelin (RDG) and κ‐carrageenan (1:2 weight ratio) dry‐heated at 60 °C and 79% relative humidity for 24 h.RESULTS: Sodium dodecyl sulfate‐polyacrylamide gel electrophoresis and Fourier transform‐infrared analysis provided evidence on the formation of the Maillard type conjugation. Amino acid analysis suggested that the major locus during the Maillard reaction were lysine and arginine. Circular dichroism spectra showed decreasing amounts of α‐helix and β‐strand in the products with increment in the amount of turns and random coil. Conjugation with κ‐carrageenan could significantly improve solubility of RDG (P < 0.05). Measurements of mean droplet size and creaming stability in oil‐in‐water emulsions showed that the conjugate was more effective at stabilizing emulsions at low pH or in the presence of high ionic strength.CONCLUSION: The Maillard reaction can be successfully used as a coupling method for RDG and κ‐carrageenan to form the conjugate with improved solubility and emulsion stabilization. Copyright © 2012 Society of Chemical Industry
Process Sensor Systems for Laser Beam Welding
Authors: Dorsch Friedhelm , Braun Holger , Keßler Steffen , Magg Winfried , Pfitzner Dieter , Plaßwich Sven 
Published: June 2012

AbstractThe use of lasers in materials processing is increasing, and in particular with the availability of more brilliant laser sources, like disk and fiber lasers, new processes and applications in laser beam welding become of interest. To take full advantage of these new capabilities the accurate tool of a high‐brilliant laser beam requires precise handling and process control. Process sensor systems are cornerstones for advanced laser welding stations that are suitable for integration in automated mass production.
Study on the Morphologies of Covalent Organic Microporous Polymers: the Role of Reaction Solvents
Authors: Tan Dazhi , Fan Wenjie , Xiong Wannan , Sun Hanxue , Cheng Yaqi , Liu Xiaoyu , Meng Changgong , Li An , Deng Wei‐Qiao 
Published: June 2012

AbstractTwo‐dimensional conjugated microporous polymers (CMPs) composed of alternative phenylene and ethynylene units are synthesized, by cross‐coupling polymerization of 1,3,5‐triethynylbenzene and 1,3,5‐tribromobenzene with various solvents. Our work shows that the morphology of CMPs is greatly affected by the choice of solvents used in synthesis. Sphere, tubular, and plate‐like structures are received by using the toluene, p‐xylene, and mesitylene solvents, respectively. Our results demonstrate that the morphology of CMPs affects the storage capacity for organic solvents remarkably, with the plate‐like CMP showing best performance. This work is expected to provide useful guidance to rationally design CMPs as absorbent materials for organic solvents.
Expression of M6 and M7 lysin in Mytilus edulis is not restricted to sperm, but occurs also in oocytes and somatic tissue of males and females
Authors: Heß Anne‐Katrin , Bartel Manuela , Roth Karina , Messerschmidt Katrin , Heilmann Katja , Kenchington Ellen , Micheel Burkhard , Stuckas Heiko 
Published: June 2012

AbstractSperm proteins of marine sessile invertebrates have been extensively studied to understand the molecular basis of reproductive isolation. Apart from molecules such as bindin of sea urchins or lysin of abalone species, the acrosomal protein M7 lysin of Mytilus edulis has been analyzed. M7 lysin was found to be under positive selection, but mechanisms driving the evolution of this protein are not fully understood. To explore functional aspects, this study investigated the protein expression pattern of M7 and M6 lysin in gametes and somatic tissue of male and female M. edulis. The study employs a previously published monoclonal antibody (G26‐AG8) to investigate M6 and M7 lysin protein expression, and explores expression of both genes. It is shown that these proteins and their encoding genes are expressed in gametes and somatic tissue of both sexes. This is in contrast to sea urchin bindin and abalone lysin, in which gene expression is strictly limited to males. Although future studies need to clarify the functional importance of both acrosomal proteins in male and female somatic tissue, new insights into the evolution of sperm proteins in marine sessile invertebrates are possible. This is because proteins with male‐specific expression (bindin, lysin) might evolve differently than proteins with expression in both sexes (M6/M7 lysin), and the putative function of both proteins in females opens the possibility that the evolution of M6/M7 lysin is under sexual antagonistic selection, for example, mutations beneficial to the acrosomal function that are less beneficial the function in somatic tissue of females.Mol. Reprod. Dev. 79: 517‐524, 2012. © 2012 Wiley Periodicals, Inc.
Developmental expression of the cellular prion protein (PrPC) in bovine embryos
Authors: Peralta Oscar A. , Huckle William R. , Eyestone Willard H. 
Published: June 2012

AbstractThe mammalian cellular prion protein (PrPC) is a highly conserved glycoprotein that may undergo conversion into a conformationally altered isoform (scrapie prion protein or PrPSc), widely believed to be the pathogenic agent of transmissible spongiform encephalopathies (TSEs). Although much is known about PrPSc conversion and its role in TSEs, the normal function of PrPC has not been elucidated. In adult mammals, PrPC is most abundant in the central nervous tissue, with intermediate levels in the intestine and heart, and lower levels in the pancreas and liver. PrPC is expressed during neurogenesis throughout development, and it has recently been proposed that PrPC participates in neural cell differentiation during embryogenesis. In order to establish the developmental timing and to address the cell‐specific expression of PrPC during mammalian development, we examined PrPC expression in bovine gametes and embryos through gestation Day 39. Our data revealed differential levels of Prnp mRNA at Days 4 and 18 in pre‐attachment embryos. PrPC was detected in the developing central and peripheral nervous systems in Day‐27, 32‐, and ‐39 embryos. PrPC was particularly expressed in differentiated neural cells located in the marginal regions of the central nervous system, but was absent from mitotically active, periventricular areas. Moreover, a PrPC cell‐specific pattern of expression was detected in non‐nervous tissues, including liver and mesonephros, during these stages. The potential participation of PrPC in neural cell differentiation is supported by its specific expression in differentiated states of neurogenesis. Mol. Reprod. Dev. 79:488–498, 2012. © Wiley Periodicals, Inc.