bluuebunny/crossref_metadata_2025_split huggingface dataset:
Toward the Control of the Creation of Mixed Monolayers on Glassy Carbon Surfaces by Amine Oxidation
Authors: Groppi Jessica , Bartlett Philip N. , Kilburn Jeremy D. 
Published: December 2015

AbstractA versatile and simple methodology for the creation of mixed monolayers on glassy carbon (GC) surfaces was developed, using an osmium–bipyridyl complex and anthraquinone as model redox probes. The work consisted in the electrochemical grafting on GC of a mixture of mono‐protected diamine linkers in varying ratios which, after attachment to the surface, allowed orthogonal deprotection. After optimisation of the deprotection conditions, it was possible to remove one of the protecting groups selectively, couple a suitable osmium complex and cap the residual free amines. The removal of the second protecting group allowed the coupling of anthraquinone. The characterisation of the resulting surfaces by cyclic voltammetry showed the variation of the surface coverage of the two redox centres in relation to the initial ratio of the linking amine in solution.
Access to Versatile β‐Cyclodextrin Scaffolds through Guest‐Mediated Monoacylation
Authors: Vurgun Nesrin , Gómez‐Biagi Rodolfo F. , Nitz Mark 
Published: December 2015

AbstractHerein, we report the selective mono‐derivatization of heptakis[6‐deoxy‐6‐(2‐aminoethylsulfanyl)]‐β‐CD (1) through a guest‐mediated covalent capture strategy. The use of guests functionalized with cleavable linkers enables the installation of an amine‐orthogonal thiol group on the primary rim of 1 as a handle for further transformations to the β‐CD scaffold. Applying this methodology, two novel monoderivatized β‐CDs were obtained in good yield and high purity. Both of these monoacylated CDs were amenable to facile linker cleavage and further modification at the resulting thiol group. This methodology can be applied towards the synthesis heterofunctionalized β‐CD constructs for analyte sensing, drug delivery, and other applications.
Magnetocaloric Properties of Heterometallic 3d–Gd Complexes Based on the [Gd(oda)3]3− Metalloligand
Authors: Qiu Jiang‐Zhen , Wang Long‐Fei , Chen Yan‐Cong , Zhang Ze‐Min , Li Quan‐Wen , Tong Ming‐Liang 
Published: December 2015

AbstractA series of heterometallic 3d–Gd3+ complexes based on a lanthanide metalloligand, [M(H2O)6][Gd(oda)3]⋅3 H2O [M=Cr3+ (1‐Cr)] (H2oda=2,2′‐oxydiacetic acid), [M(H2O)6][MGd(oda)3]2⋅3 H2O [M=Mn2+ (2‐Mn), Fe2+ (2‐Fe) and Co2+ (2‐Co)], and [M3Gd2(oda)6(H2O)6]⋅12 H2O [M=Ni2+ (3‐Ni), Cu2+ (3‐Cu), and Zn2+ (3‐Zn)], are reported. Magnetic and heat‐capacity studies revealed a significant impact on the magnetocaloric effect depending on the anisotropy of the 3d transition metal ions, as confirmed by comparison of the observed maximum values of −ΔSm between complexes 2‐Co and 1‐Cr. In these two complexes, the 3d metal ions have the same spin (S=3/2 for Co2+ and Cr3+ ions), and the theoretical calculation suggested a larger −ΔSm value for 2‐Co (47.8 J K−1 kg−1) than 1‐Cr (37.5 J K−1 kg−1); however, the significant anisotropy of Co2+ ions in 2‐Co, which can result in smaller effective spins, gives a smaller value of −ΔSm for 2‐Co (32.2 J K−1 kg−1) than for 1‐Cr (35.4 J K−1 kg−1) at ΔH=9 T.
[4+3] Cycloaddition of Donor–Acceptor Cyclopropanes with Amphiphilic Benzodithioloimine as Surrogate for ortho‐Bisthioquinone
Authors: Garve Lennart K. B. , Pawliczek Martin , Wallbaum Jan , Jones Peter G. , Werz Daniel B. 
Published: December 2015

AbstractDonor–acceptor cyclopropanes were reacted with amphiphilic benzodithioloimine to give seven‐membered heterocycles with two sulfur atoms. Formally, this transformation can be regarded as a [4+3] cycloaddition reaction of the three‐membered ring and ortho‐bisthioquinone. The benzodithioloimine serves as a surrogate for this highly reactive diene. The structure of the products was confirmed by X‐ray crystallography. Broad signals in 13C NMR studies suggest that several conformers, slowly interconverting on the NMR timescale, are present at room temperature.
Absolute Configuration Assignment of a Paraconic Acid Derivative via Vibrational Circular Dichroism Spectroscopy and Density Functional Theory Calculation
Authors: Meninno Sara , Rizzo Paola , Abbate Sergio , Longhi Giovanna , Mazzeo Giuseppe , Monaco Guglielmo , Lattanzi Alessandra , Zanasi Riccardo 
Published: December 2015

AbstractDensity functional theory calculation of the vibrational circular dichroism spectrum was used to assign the absolute configuration of an all‐carbon quaternary β‐stereocenter of a γ‐butyrolactone recently synthesized through an asymmetric organocatalytic tandem aldol/lactonization sequence. Comparison with the experimental spectrum is satisfactory, on account of the fact that spectroscopic features are weak due to the presence of multiple conformers. As a result, the (R) absolute configuration was assigned to the (+) optical isomer. Chirality 28:110–115, 2016. © 2015 Wiley Periodicals, Inc.
Towards the Limits of Vibrational Circular Dichroism Spectroscopy: VCD Spectra of Some Alkyl Vinylethers
Authors: Zinna Francesco , Pescitelli Gennaro 
Published: December 2015

AbstractThree alkyl vinylethers from our collection of chiral samples were investigated through VCD spectroscopy, in combination with Density Functional Theory (DFT) calculations. Despite the simplicity of the compounds, reproducing all the spectral features is an involved task, since the many significantly populated conformers contribute to the total VCD spectrum with bands which often have opposite signatures. Nevertheless, we show that certain bands can be satisfactorily reproduced by calculation and therefore they may be employed for the determination of absolute configuration in these and similar compounds, for which no simple alternative method is available. Chirality 28:143–146, 2016. © 2015 Wiley Periodicals, Inc.
Separation of Enantiomers by Inclusion Gas Chromatography: On the Influence of Water in the Molecular Complexation of Methyl 2‐Chloropropanoate Enantiomers and the Modified γ‐Cyclodextrin Lipodex‐E
Authors: Mandoli Alessandro , Schurig Volker 
Published: December 2015

AbstractA profound influence of water has previously been detected in the complexation of the enantiomers of methyl 2‐chloropropanoate (MCP) and the chiral selector octakis(3‐O‐butanoyl‐2,6‐di‐O‐pentyl)‐γ‐cyclodextrin (Lipodex‐E) in NMR and sensor experiments. We therefore investigated the retention behavior of MCP enantiomers on Lipodex‐E by gas chromatography (GC) under hydrous conditions. Addition of water to the N2 carrier gas modestly reduced the retention factors k of the enantiomers, notably for the second eluted enantiomer (S)‐MCP. This resulted in an overall decrease of enantioselectivity ‐ΔS,R(ΔG) in the presence of water. The effect was fully reversible. Consequently, for a conditioned column in the absence of residual water, the determined thermodynamic data, i.e. ΔS,R(ΔH) = –12.64 ± 0.08 kJ mol‐1 and ΔS,R(ΔS) = –28.18 ± 0.23 J K‐1 mol‐1, refer to a true 1:1 complexation process devoid of hydrophobic hydration. Chirality 28:124–131, 2015. © 2015 Wiley Periodicals, Inc.
Increasing the Energy Efficiency of Batch‐Type Drying with Partial Air Recirculation
Authors: Ziegler Thomas , Jubaer Hasan , Schütz Marco 
Published: December 2015

AbstractPartial recirculation of the dryer outlet air is a common practice in many batch‐type drying processes. However, energy consumption and total duration of drying are directly affected by the recycled air ratio (RAR). In order to assess the influence of different ambient air conditions on favorable values of RAR, a new quantity is introduced. The so‐called critical drying efficiency determines the most favorable starting point for partial air recirculation. It is shown that by increasing RAR successively in the further course of drying, substantial energy savings can be achieved with only a marginal extension of drying duration. It is also pointed out that optimized control of drying plants should be based not only on dryer outlet air conditions but also on ambient air conditions.
Fighting Cancer with Transition Metal Complexes: From Naked DNA to Protein and Chromatin Targeting Strategies
Authors: Palermo Giulia , Magistrato Alessandra , Riedel Tina , von Erlach Thibaud , Davey Curt A. , Dyson Paul J. , Rothlisberger Ursula 
Published: December 2015

AbstractMany transition metal complexes have unique physicochemical properties that can be efficiently exploited in medicinal chemistry for cancer treatment. Traditionally, double‐stranded DNA has been assumed to be the main binding target; however, recent studies have shown that nucleosomal DNA as well as proteins can act as dominant molecular binding partners. This has raised new questions about the molecular determinants that govern DNA versus protein binding selectivity, and has offered new ways to rationalize their biological activity and possible side effects. To address these questions, molecular simulations at an atomistic level of detail have been used to complement, support, and rationalize experimental data. Herein we review some relevant studies—focused on platinum and ruthenium compounds—to illustrate the power of state‐of‐the‐art molecular simulation techniques and to demonstrate how the interplay between molecular simulations and experiments can make important contributions to elucidating the target preferences of some promising transition metal anticancer agents. This contribution aims at providing relevant information that may help in the rational design of novel drug‐discovery strategies.
The Three Possible 2‐(Pyrenylethynyl) Adenosines: Rotameric Energy Barriers Govern the Photodynamics of These Structural Isomers
Authors: Reuss Andreas J. , Grünewald Christian , Braun Markus , Engels Joachim W. , Wachtveitl Josef 
Published: December 2015

AbstractThis article presents a comprehensive study of the photophysics of 2‐(2‐pyrenylethynyl) adenosine and 2‐(4‐pyrenylethynyl) adenosine, which are structural isomers of the well‐established fluorescent RNA label 2‐(1‐pyrenylethynyl) adenosine. We performed steady‐state and ultrafast transient absorption spectroscopy studies along with time‐resolved fluorescence emission experiments in different solvents to work out the interplay of locally excited and charge‐transfer states. We found the ultrafast photodynamics to be crucial for the fluorescence decay behavior, which extends up to tens of nanoseconds and is partially multi‐exponential. These features in the ultrafast dynamics are indicative of the rotational energy barriers in the first excited state.
Reply to Pardo et al. 2015 on ‘Reply to comment on Couto‐Mendoza et al. 2014. More complexity does not always mean more accuracy: the case of IBMWP and METI in NW Spain’ Ecohydrology DOI: 10.1002/eco.1660
Authors: Couto‐Mendoza M.T. , Vieira‐Lanero R. , Cobo F. 
Published: December 2015

AbstractThe manuscript “More complexity does not always mean more accuracy: the case of IBMWP and METI in NW Spain” compares the behaviour of one multimetric index (METI), proposed for NW Spain rivers, and the IBMWP, excluded from the Spanish Water Planning Instruction for NW Spain rivers, under the same conditions in the Miño‐Sil Basin District (DHMS) in the NW Spain. The conclusion of that assay is that both indices are useful tools for evaluating the ecological status of the running‐water ecosystems in the NW Spain, and emphasises the use of the IBMWP, because it may be better (more practical) than the METI, which has already been proposed for the same goal in this region. Another topic to deal with in the report was the number of established reference sites in the DHMS. Pardo et al. () give 5 replies to 5 criticisms that question the use of the METI in the NW Spain. Pardo et al. (2015) mention that those criticisms are contained in Couto‐Mendoza et al. (). Overall, Pardo et al. () highlight the validity of the METI as a method for assessing the ecological status because, unlike the IBMWP that they reject, it has been intercalibrated in the European exercise in the Central Baltic Rivers GIG. Each reply to the criticisms selected by Pardo et al. () is discussed. Copyright © 2015 John Wiley & Sons, Ltd.
Non‐steroidal mineralocorticoid receptor antagonism for the treatment of cardiovascular and renal disease
Authors: Bramlage Peter , Swift Stephanie L. , Thoenes Martin , Minguet Joan , Ferrero Carmen , Schmieder Roland E. 
Published: December 2015

AbstractPharmaceutical antagonism of the mineralocorticoid receptor (MR) can protect against organ damage caused by elevated aldosterone levels in patients experiencing heart failure (HF), chronic kidney disease (CKD), primary aldosteronism, and hypertension. While traditional steroid‐based MR antagonists effectively reduce mortality rates and extend patient survival, their broad application has been limited by significant side effects, most notably hyperkalaemia. Recently, finerenone (BAY 94‐8862) has emerged as a next‐generation non‐steroidal dihydropyridine‐based MR antagonist designed to minimize off‐target effects while maintaining potent efficacy. In this review, the outcomes of finerenone therapy in several diseases associated with MR activity are explored. The (pre‐) clinical efficacy of finerenone is compared with that of traditional steroid‐based MR antagonists. Finally, recent and ongoing clinical trials using finerenone to treat chronic HF, CKD, and diabetic nephropathy are discussed. Taken together, pre‐clinical and clinical evidence suggests that finerenone may achieve equivalent organ‐protective effects with reduced levels of electrolyte disturbance compared with traditional steroid‐based MR antagonists. This supports further clinical development of finerenone for the treatment of cardiovascular and renal disease.
Early right ventricular response to cardiac resynchronization therapy: impact on clinical outcomes
Authors: Stolfo Davide , Tonet Elisabetta , Merlo Marco , Barbati Giulia , Gigli Marta , Pinamonti Bruno , Ramani Federica , Zecchin Massimo , Sinagra Gianfranco 
Published: December 2015

AbstractAimsRight ventricular (RV) dysfunction has been associated with a worse outcome in heart failure patients undergoing CRT. However, evidence on the RV response to CRT is controversial and there are no data regarding the early effects of CRT on RV function (RVF). We sought to investigate whether a CRT device favourably influences the RVF acutely after implantation, impacting on long‐term outcomes.Methods and resultsPatients who successfully underwent CRT device implantation from January 2005 to January 2014 were retrospectively analysed. RV dysfunction was defined by an RV fractional area change <35%. Post‐procedural echocardiographic evaluation was performed at a median time of 2 days (interquartile range 1–6 days). The primary endpoint was a composite of all‐cause mortality and urgent heart transplantation. A total of 194 patients with available pre‐ and post‐procedural RVF assessment were included. Sixty‐two (32%) presented an impaired RVF before the procedure. Of them, 32% showed prompt normalization of RVF following CRT. This occurred in parallel with a large improvement in pulmonary arterial pressure, mitral regurgitation, E/E′ ratio, and diastolic function. Pre‐implantation independent predictors of early RVF normalization were LBBB (P = 0.034) and higher systolic blood pressure (P = 0.026). Improvement in RVF was independently associated with a better long‐term prognosis at multivariable analysis [hazard ratio 0.124; 95% confidence interval 0.016–0.966, P = 0.04).ConclusionsAcute normalization of RVF can be observed after CRT along with haemodynamic improvement, and therefore can be used as an independent predictor of transplant‐free survival.
Concentrations of polycyclic aromatic hydrocarbons in New York City community garden soils: Potential sources and influential factors
Authors: Marquez-Bravo Lydia G. , Briggs Dean , Shayler Hannah , McBride Murray , Lopp Donna , Stone Edie , Ferenz Gretchen , Bogdan Kenneth G. , Mitchell Rebecca G. , Spliethoff Henry M. 
Published: December 2015

Abstract

A total of 69 soil samples from 20 community gardens in New York City (New York, USA) were collected and analyzed for 23 polycyclic aromatic hydrocarbons (PAHs) and black carbon. For each garden, samples were collected from nongrowing areas (non-bed) and from vegetable-growing beds, including beds with and without visible sources of PAHs. The sum of the US Environmental Protection Agency's 16 priority PAHs ranged up to 150 mg/kg, and the median (5.4 mg/kg) and mean (14.2 mg/kg) were similar to those previously reported for urban areas in the northeast United States. Isomer ratios indicated that the main sources of PAHs were petroleum, coal, and wood combustion. The PAH concentrations were significantly and positively associated with black carbon and with modeled air PAH concentrations, suggesting a consistent relationship between historical deposition of atmospheric carbon-adsorbed PAHs and current PAH soil concentrations. Median PAH soil concentration from non-bed areas was higher (7.4 mg/kg) than median concentration from beds in the same garden (4.0 mg/kg), and significantly higher than the median from beds without visible sources of PAHs (3.5 mg/kg). Median PAH concentration in beds from gardens with records of soil amendments was 58% lower compared with beds from gardens without those records. These results suggest that gardening practices in garden beds without visible sources of PAHs contribute to reduce PAH soil concentrations. Environ Toxicol Chem 2016;35:357–367. © 2015 SETAC
Net methylmercury production in 2 contrasting stream sediments and associated accumulation and toxicity to periphyton
Authors: Klaus Jaclyn E. , Hammerschmidt Chad R. , Costello David M. , Burton G. Allen 
Published: December 2015

Abstract

Periphyton uptake of bioaccumulative methylmercury (MeHg) may be an important entryway into the food web of many stream ecosystems where periphyton can be dominant primary producers. The net production of MeHg in stream sediment, its bioaccumulation in periphyton, and the potential toxicity of divalent Hg (Hg[II]) and MeHg in sediment to periphyton were investigated with a 67-d in situ incubation experiment using chemical exposure substrates containing either a fine-grained, organic-rich or a sandy, low-organic sediment, each amended with varying concentrations of mercuric chloride. Methylmercury was produced in sediment, and concentrations increased with greater amounts of added Hg(II); however, the net production of MeHg was inhibited in the highest Hg(II) treatments of both sediments. The range of total Hg concentrations that inhibited MeHg production was between approximately 80 000 ng Hg and 350 000 ng Hg per gram of organic matter for both sediments. Periphyton colonizing substrates accumulated MeHg in proportion to the concentration in sediment, but periphyton exposed to the sandy sediment accumulated approximately 20-fold more than those exposed to the organic-rich sediment relative to sediment MeHg concentrations. Toxicity of either Hg(II) or MeHg to periphyton was not observed with either periphyton organic content, net primary production, or respiration as endpoints. These results suggest that in situ production and bioaccumulation of MeHg in stream ecosystems can vary as a function of sediment characteristics and Hg(II) loadings to the sediment. Environ Toxicol Chem 2016;35:1759–1765. © 2015 SETAC
Pharmacokinetics, Pharmacodynamics, Safety, and Clinical Activity of Multiple Doses of RCT‐18 in Chinese Patients With Systemic Lupus Erythematosus
Authors: Zhao Qian , Chen Xia , Hou Yong , Jiang Ji , Zhong Wen , Yao Xuejing , Wang Wenxiang , Li Lin , Fang Jianmin , Zhang Fengchun , Hu Pei 
Published: December 2015

AbstractRCT‐18 is a novel recombinant fusion protein that blocks the activity of a B‐lymphocyte stimulator and a proliferation‐inducing ligand. This was a randomized, single‐blind, and placebo‐controlled phase 1 study in 12 patients with systemic lupus erythematosus. Eligible patients were randomized 3:1 to receive multiple subcutaneous doses of RCT‐18 for 4 weeks (180 mg, once weekly) or placebo and monitored over an 84‐day observation period for pharmacokinetics, pharmacodynamics, immunogenicity, safety, and clinical activity. After multiple‐dose RCT‐18, the maximal serum concentration (Cmax) of total and free RCT‐18 was reached within 1 to 2 days. Mean elimination half‐life for total RCT‐18 and free RCT‐18 was 11.4 to 26.4 days and 2.4 to 26.5 days, respectively. Slight accumulation was found after multiple subcutaneous administrations. The average accumulation ratios of AUC and Cmax after the fourth administration of RCT‐18 were 2.0 and 1.7 for total RCT‐18, and 1.8 and 1.6 for free RCT‐18. The formation and elimination of BLyS‐RCT‐18 complex were much slower, with a time to Cmax of 14 to 46 days. Pharmacokinetic characteristics of RCT‐18 in SLE patients were similar to those in patients with rheumatoid arthritis. No positive reaction was detected in the immunogenicity assessments. RCT‐18 was biologically active, according to serum immunoglobulin and B‐cell levels. Treatment‐related IgM and IgA reduction was found during this study. CD19+, IgD+, and CD27+ B‐cell counts were increased after administration and decreased subsequently. SLE patients treated with RCT‐18 were more prone to infections, including moderate and severe infections. Lower dosages of RCT‐18 should be considered in further clinical development.