bluuebunny/crossref_metadata_2025 huggingface dataset:
Identification of anti‐inflammatory active ingredients from Tumuxiang by ultra‐performance liquid chromatography/quadrupole time‐of‐flight‐MSE
Authors: Gao Xia , Ma Yuling , Wang Zhuowei , Bia Ruibin , Zhang Pei , Hu Fangdi
Published: December 2017

The dried roots of Inula helenium L. (IH) and Inula racemosa Hook f. (IR) are used commonly as folk medicine as ‘tumuxiang’ (TMX). The mixing and sharing of IH and IR in clinical use is a universal phenomenon. Modern pharmacological studies confirmed that IH and IR display anti‐inflammatory activities. However, the difference in anti‐inflammatory pharmacodynamic substances between these two herbs is still unknown. In the present study, the fingerprints of 18 IH and nine IR samples were established using UPLC/QTOF‐MSE. A dimethylbenzene‐induced mouse ear vasodilation model was applied in evaluating the anti‐inflammatory properties of all 27 samples. Then, the spectrum–efficacy model between chemical characteristic peaks and anti‐inflammatory activities was investigated using principal component regression and partial least squares. Finally, the combination of UNIFI Scientific Information System with a library search of traditional Chinese medicines was employed to automatically characterize the peaks. UNIFI identified a total of 80 chemical components. Among the components, the 53 characteristic peaks showed correlation with anti‐inflammatory activities, pointing to phenolic and organic acids as primary anti‐inflammatory ingredients of TMX. This approach can efficiently and intelligently facilitate the identification of bioactive components from traditional Chinese medicine.
UPLC‐MS/MS based diagnostics for epithelial ovarian cancer using fully sialylated C4‐binding protein
Authors: Tanabe Kazuhiro , Matsuo Koji , Miyazawa Masaki , Hayashi Masaru , Ikeda Masae , Shida Masako , Hirasawa Takeshi , Sho Ryuichiro , Mikami Mikio
Published: December 2017

Serum levels of fully sialylated C4‐binding protein (FS‐C4BP) are remarkably elevated in patients with epithelial ovarian cancer (EOC) and can be used as a marker to distinguish ovarian clear cell carcinoma from endometrioma. This study aimed to develop a stable, robust and reliable liquid chromatography–hybrid mass spectrometry (UPLC‐MS/MS) based diagnostic method that would generalize FS‐C4BP as a clinical EOC biomarker. Glycopeptides derived from 20 μL of trypsin‐digested serum glycoprotein were analyzed via UPLC equipped with an electrospray ionization time‐of‐flight mass spectrometer. This UPLC‐MS/MS‐based diagnostic method was optimized for FS‐C4BP and validated using sera from 119 patients with EOC and 127 women without cancer. A1958 (C4BP peptide with two fully sialylated biantennary glycans) was selected as a marker of FS‐C4BP because its level in serum was highest among FS‐C4BP family members. Preparation and UPLC‐MS/MS were optimized for A1958, and performance and robustness were significantly improved relative to our previous method. An area under the curve analysis of the FS‐C4BP index receiver operating characteristic curve revealed that the ratio between A1958 and A1813 (C4BP peptide with two partially sialylated biantennary glycans) reached 85%. A combination of the FS‐C4BP index and carbohydrate antigen‐125 levels further enhanced the sensitivity and specificity.
Heat Shock Proteins Revisited: Using a Mutasynthetically Generated Reblastatin Library to Compare the Inhibition of Human and Leishmania Hsp90s
Authors: Mohammadi‐Ostad‐Kalayeh Sona , Stahl Frank , Scheper Thomas , Kock Klaus , Herrmann Christian , Heleno Batista Fernanda Aparecida , Borges Júlio César , Sasse Florenz , Eichner Simone , Ongouta Jekaterina , Zeilinger Carsten , Kirschning Andreas
Published: December 2017

Thirteen new reblastatin derivatives, with alkynyl, amino and fluoro substituents on the aromatic ring, were prepared by a chemo‐biosynthetic approach using an AHBA(−) mutant strain of Streptomyces hygroscopicus, the geldanamycin producer. The inhibitory potencies of these mutaproducts and of an extended library of natural products and derivatives were probed with purified heat shock proteins (Hsps), obtained from Leishmania braziliensis (LbHsp90) as well as from human sources (HsHsp90). We determined the activities of potential inhibitors by means of a displacement assay in which fluorescence‐labelled ATP competes for the ATP binding sites of Hsps in the presence of the inhibitor in question. The results were compared with those of cell‐based assays and, in selected cases, of isothermal titration calorimetry (ITC) measurements. In essence, reblastatin derivatives are also able to bind effectively to the ATP‐binding site of LbHsp90, and for selected derivatives, moderate differences in binding to LbHsp90 and HsHsp90 were encountered. This work demonstrates that parasitic heat shock proteins can be developed as potential pharmaceutical targets.
Silica‐Grafted Neodymium Catalysts for the Production of Ultrahigh‐Molecular‐Weight cis‐1,4‐Polyisoprene
Authors: Le Roux Erwan , Liang Yucang , Anwander Reiner
Published: December 2017

Supported neodymium‐based Ziegler‐type catalysts are obtained by grafting homoleptic methylaluminate Nd(AlMe4)3 onto high‐surface silica materials including periodic mesoporous silicas MCM‐41, SBA‐15, and KIT‐6. Low [Et2AlCl]‐cocatalyst contents allow for the fabrication of polyisoprenes with ultrahigh molecular weight (UHMWPI). The synthetic rubbers display molecular weights as high as 3×106 g mol−1, polydispersity indices as low as 1.2, and microstructures with 99 % cis‐stereospecificity. Combined analysis of the organolanthanide/silica hybrid materials by nitrogen physisorption, FTIR and magic angle spinning NMR spectroscopies, and elemental (metal) analysis assist in elucidating the intrapore surface organometallic chemistry and suggest the formation of unprecedented organolanthanide species.
Sol–gel Entrapped Nitroxyl Radicals: Catalysts of Broad Scope
Authors: Ciriminna Rosaria , Pandarus Valerica , Béland Francois , Pagliaro Mario
Published: December 2017

Sol–gel entrapped TEMPO‐like radicals are excellent supported molecular catalysts for the selective and clean alcohol oxidation, including the primary hydroxyl functions of cellulose. Could these materials reach widespread utilization for the synthesis of fine chemicals, bio‐based building blocks and even carboxyl cellulose nanofibrils? This study offers a critical perspective.
Effect of Different Cosolvents on Transesterification of Waste Cooking Oil in a Microreactor
Authors: Aghel Babak , Mohadesi Majid , Sahraei Sasan
Published: December 2017

Biodiesel was prepared from waste cooking oil combined with methanol. The process was performed via transesterification in a microreactor using kettle limescale as a heterogeneous catalyst and various cosolvents under different conditions. n‐Hexane and tetrahydrofuran were selected as cosolvents to investigate fatty acid methyl esters (FAMEs). To optimize the reaction conditions, the main parameters affecting FAME% including reaction temperature, catalyst concentration, oil‐to‐methanol volumetric ratio, and cosolvent‐to‐methanol volumetric ratio were studied via response surface methodology. Under optimal reaction conditions and in the presence of the cosolvents n‐hexane and tetrahydrofuran, high FAME purities were achieved. Considering the experimental results, the limescale catalyst is a unique material, and the cosolvent method can reduce significantly the reaction time and biodiesel production cost.
Permeability of a Fumasep‐FAD Membrane for Selected Inorganic Acids
Authors: Palatý Zdeněk , Bendová Helena
Published: December 2017

Salt and acid‐containing mixtures can effectively be separated by processes based on polymeric ion‐exchange membranes, especially diffusion dialysis. The transport of selected inorganic acids (HCl, HF, HNO3, and H2SO4) through an anion‐exchange membrane Fumasep‐FAD was experimentally studied in a two‐compartment batch dialyzer. The process was quantified by permeability of the membrane obtained from the dependences of the acid concentrations and liquid volumes upon time in both compartments of the dialyzer. The experiments revealed that this membrane is highly permeable for the acids investigated.
Investigations of the Copper‐Catalyzed Oxidative Cross‐Coupling of Tetrahydroisoquinolines with Diethylzinc by a Combination of Mass Spectrometric and Electrochemical Methods
Authors: Willms J. Alexander , Gleich Hermann , Schrempp Michael , Menche Dirk , Engeser Marianne
Published: December 2017

The aerobic oxidative cross‐coupling of tetrahydroisoquinolines (THIQs) with diethylzinc catalyzed by CuCl2 has been examined by means of electrospray mass spectrometry (ESI‐MS). Substrates, intermediates, and the product were readily detected. Particular emphasis has been placed on the role of CuCl2. Formation of the intermediate iminium species has been investigated in more detail by ESI‐MS, electrochemistry‐coupled ESI mass spectrometry (EC‐MS), and cyclic voltammetry (CV). Our experiments have consistently revealed strong influences of the N‐substituent of the THIQ derivative and its oxidation stability with respect to CuCl2. The results may help to expand the synthetic scope of the reaction, while also further establishing EC‐MS as a valuable technique for linking mass spectrometry with cyclic voltammetry in mechanistic studies of organic redox reactions.
Stimulus‐Responsive Assembly of Nanoparticles using Host–Guest Interactions of Cyclodextrins
Authors: Engel Sabrina , Möller Nadja , Ravoo Bart Jan
Published: December 2017

The design of multifunctional nanomaterials that respond to external stimuli and mimic the capacity of biological materials to respond and adapt to their environment has become a focus of interest in nanotechnology. In this Concept, we describe the development of supramolecular nanoparticle assemblies constructed by use of host–guest interactions between cyclodextrins and suitable guest molecules. The nanoparticle assembly is reversible and can be directed by applying different stimuli that act either on the guest molecules or the nanoparticles. This strategy can be extended to mesoscale assembly of microparticles. We highlight the newest research work in this field of nanochemistry and point out future perspectives and opportunities.
Cyclobutanone Mimics of Intermediates in Metallo‐β‐Lactamase Catalysis
Authors: Abboud Martine I. , Kosmopoulou Magda , Krismanich Anthony P. , Johnson Jarrod W. , Hinchliffe Philip , Brem Jürgen , Claridge Timothy D. W. , Spencer James , Schofield Christopher J. , Dmitrienko Gary I.
Published: December 2017

The most important resistance mechanism to β‐lactam antibiotics involves hydrolysis by two β‐lactamase categories: the nucleophilic serine and the metallo‐β‐lactamases (SBLs and MBLs, respectively). Cyclobutanones are hydrolytically stable β‐lactam analogues with potential to inhibit both SBLs and MBLs. We describe solution and crystallographic studies on the interaction of a cyclobutanone penem analogue with the clinically important MBL SPM‐1. NMR experiments using 19F‐labeled SPM‐1 imply the cyclobutanone binds to SPM‐1 with micromolar affinity. A crystal structure of the SPM‐1:cyclobutanone complex reveals binding of the hydrated cyclobutanone through interactions with one of the zinc ions, stabilisation of the hydrate by hydrogen bonding to zinc‐bound water, and hydrophobic contacts with aromatic residues. NMR analyses using a 13C‐labeled cyclobutanone support assignment of the bound species as the hydrated ketone. The results inform on how MBLs bind substrates and stabilize tetrahedral intermediates. They support further investigations on the use of transition‐state and/or intermediate analogues as inhibitors of all β‐lactamase classes.
Liquid chromatographic separation and thermodynamic investigation of lorcaserin hydrochloride enantiomers on immobilized amylose–based chiral stationary phase
Authors: Wani Dattatraya V. , Rane Vipul P. , Mokale Santosh N.
Published: December 2017

A novel liquid chromatographic method was developed for enantiomeric separation of lorcaserin hydrochloride on Chiralpak IA column containing chiral stationary phase immobilized with amylose tris (3.5‐dimethylphenylcarbamate) as chiral selector. Baseline separation with resolution greater than 4 was achieved using mobile phase containing mixture of n‐hexane/ethanol/methanol/diethylamine (95:2.5:2.5:0.1, v/v/v/v) at a flow rate of 1.2 mL/min. The limit of detection and limit of quantification of the S‐enantiomer were found to be 0.45 and 1.5 μg/mL, respectively; the developed method was validated as per ICH guideline. The influence of column oven temperatures studied in the range of 20°C to 50°C on separation was studied; from this, retention, separation, and resolution were investigated. The thermodynamic parameters ΔH°, ΔS°, and ΔG° were evaluated from van't Hoff plots,(Ink′ versus 1/T) and used to explain the strength of interaction between enantiomers and immobilized amylose–based chiral stationary phase
The Impact of E‐Mobility in a Future Energy System Dominated by Renewable Electricity
Authors: Bünger Ulrich , Michalski Jan
Published: December 2017

Battery and fuel cell electric cars have been identified as solution to meet the target of reducing greenhouse gas emissions by 80 to 95 % before 2050, however they will also impact the increasingly renewable electricity‐based energy system. A numerical case study is conducted for a prototypical station consisting of hydrogen refueling equipment for fuel cell electric vehicles and charging points for battery electric vehicles located in Northern Germany with rather good wind but limited photovoltaics conditions. Major conclusions for the impact of both e‐mobility concepts on the energy system are drawn.
Population Pharmacokinetics of Levofloxacin in Plasma and Bone of Patients Undergoing Hip or Knee Surgery
Authors: Gergs Ulrich , Ihlefeld Dorothea , Clauss Tobias , Weiss Michael , Pönicke Klaus , Hofmann Gunther O. , Neumann Joachim
Published: December 2017

Patients undergoing hip or knee replacement therapy are routinely pretreated with antibiotics before they enter the operation theater. This treatment intends to reduce the incidence of peri‐ or postsurgical infections. Here, we calculated the uptake kinetics of levofloxacin into bone to see whether levofloxacin could be obtained from the trabecular and cortical bone and at what time concentrations are sufficiently high to inhibit the usual hospital infections. Patients (n = 42) undergoing routine surgery were treated with 500 mg levofloxacin intravenously immediately prior to the operation. Plasma samples were taken before and at 3 points after termination of drug infusion. After replacement of the bones, extracts were obtained from them. Levofloxacin was quantified using high‐performance liquid chromatography. The kinetics of levofloxacin and its distribution into bone were analyzed using a population approach (ADAPT5). Clearance was 14.0 L/h, and distribution volume was 77 L. Bone uptake t½ was calculated as 4.2 and 5.4 hours for cortical bone and trabecular bone, respectively. In knee samples (but not in hip samples), we noted that the cortical bone contained higher levels of levofloxacin than the trabecular bone. From our data, we can conclude that levofloxacin might be useful for prophylactic use in bone surgery.
Tile/line access cache memory based on a multi‐level Z‐order tiling data layout
Authors: Wang Baokang , Fukazawa Yuki , Kondo Toshio , Sasaki Takahiro
Published: December 2017

Ineffective column‐directional cache memory access has become a bottleneck for efficient two‐dimensional (2‐D) data processing utilizing extended single instruction multiple data (SIMD) instructions. To solve this problem, we propose a cache memory with tile (column and row directions) and line (row direction) accessibility for efficient 2‐D data processing. 2‐D data access to the proposed cache memory is enabled via a hardware‐based multi‐mode address translation unit that eliminates the overhead of software‐based address calculation. To reduce the hardware overhead of the proposed cache, we propose a tag memory reduction method that replaces multiple tiles with an aligned tile set (RATS) in the cache. To verify the feasibility of the proposed cache, an LSI layout of a SIMD‐based general purpose‐oriented datapath embedding the proposed cache is designed in a 2.5×5 mm2 area using 0.18‐μm CMOS technology. Under a 3.9‐ns clock period (250 MHz), the read latency is limited to 3 clock cycles, which is the same as that for the conventional cache memory. Using the RATS method, the entire hardware overhead of the proposed cache is reduced to only 7% of that required for a conventional cache. In addition, simulation results for the proposed cache indicate a considerable reduction of L1 and L2 cache confliction misses compared with a conventional cache in power‐of‐two matrix size due to the column‐directional address stride being sufficiently smaller than page size. Therefore, the proposed cache provides efficient column‐directional parallel access as same as row‐directional parallel access so that it enables efficient SIMD operation requiring no transposition in matrix multiplication (MM). For LU decomposition (LUD), the proposed cache can provide almost the same performance to the column‐major–based LUD program as that to the row‐major–based LUD program. These results show that the proposed cache does not restrict our freedom in selecting either row‐ or column‐major order coding.
A Systematic Study of Isomorphically Substituted H‐MAlPO‐5 Materials for the Methanol‐to‐Hydrocarbons Reaction
Authors: Mortén Magnus , Mentel Łukasz , Lazzarini Andrea , Pankin Ilia A. , Lamberti Carlo , Bordiga Silvia , Crocellà Valentina , Svelle Stian , Lillerud Karl Petter , Olsbye Unni
Published: December 2017

Substituting metals for either aluminum or phosphorus in crystalline, microporous aluminophosphates creates Brønsted acid sites, which are well known to catalyze several key reactions, including the methanol to hydrocarbons (MTH) reaction. In this work, we synthesized a series of metal‐substituted aluminophosphates with AFI topology that differed primarily in their acid strength and that spanned a predicted range from high Brønsted acidity (H‐MgAlPO‐5, H‐CoAlPO‐5, and H‐ZnAlPO‐5) to medium acidity (H‐SAPO‐5) and low acidity (H‐TiAlPO‐5 and H‐ZrAlPO‐5). The synthesis was aimed to produce materials with homogenous properties (e.g. morphology, crystallite size, acid‐site density, and surface area) to isolate the influence of metal substitution. This was verified by extensive characterization. The materials were tested in the MTH reaction at 450 °C by using dimethyl ether (DME) as feed. A clear activity difference was found, for which the predicted stronger acids converted DME significantly faster than the medium and weak Brønsted acidic materials. Furthermore, the stronger Brønsted acids (Mg, Co and Zn) produced more light alkenes than the weaker acids. The weaker acids, especially H‐SAPO‐5, produced more aromatics and alkanes, which indicates that the relative rates of competing reactions change upon decreasing the acid strength.
Inhibitors and facilitators of compassion‐focused imagery in personality disorder
Authors: Naismith Iona , Mwale Amanda , Feigenbaum Janet
Published: December 2017

Background

Compassion‐focused therapy (CFT) has potential to benefit clients with a personality disorder (PD), given the inflated levels of shame and self‐criticism in this population. However, clinical observation indicates that clients with PD may find techniques from this approach challenging.

Aims

The aim of this study is to trial one aspect of CFT, compassion‐focused imagery (CFI), with this population, and identify factors that predict clients' ability to generate CFI and experience self‐compassion during the task, including type of CFI exercise and, second, to establish whether CFI outcomes increase with practice.

Method

In Study 1, 53 participants with a diagnosis of PD completed measures of self‐compassion, self‐reassurance, shame, self‐criticism, fear of self‐compassion, affect, anxious and avoidant attachment, and mental imagery abilities. Participants were assigned to trial CFI from memory (n = 25) or from imagination (n = 28), then rated their image's vividness, its compassionate traits, and ease of experiencing compassion. A negative mood manipulation was carried out, and CFI tasks and outcome measures were repeated. For Study 2, self‐compassion and self‐criticism were measured before and after 1 week of daily CFI practice.

Results

Study 1 found that negative mood and low mental imagery ability are significant inhibitors to generating compassionate images and affect. The 2 CFI exercises were equally effective. Study 2 suffered from high attrition, but regular practice was associated with significant improvement in self‐compassion (though not self‐criticism).

Conclusions

CFI appears to be effective in improving self‐compassion for some clients. However, it is less effective in the presence of negative affect. Clients with low mental imagery ability may benefit more from alternative CFT techniques.
Functionalization and Properties of Tetrahydronaphtho[2,1‐a]azulene Photoswitches
Authors: Sonne Kirstine , Lindbæk Broman Søren , Drøhse Kilde Martin , Ugleholdt Petersen Anne , Nielsen Mogens Brøndsted
Published: December 2017

Here we present a synthetic procedure for regioselectively functionalizing the tetrahydronaphtho[2,1‐a]azulene (THNA) photoswitch in its seven‐membered ring (position C10). Bromination of the C10–C11 positions occurred with excellent selectivity when using carbondisulfide as solvent at room temperature. Elimination of HBr provided a C10 bromo‐substituted THNA that could be arylated by Suzuki cross‐coupling reactions. A series of arylated compounds was prepared and subjected to switching studies. Upon irradiation, the five‐membered ring underwent ring‐opening to a product that at room temperature underwent almost instantaneous ring‐closure. By following the conversion at low temperature by UV/Vis absorption spectroscopy, we could elucidate the influence of aryl donor and acceptor groups. Thus, with a donating methoxyphenyl substituent, the ultrafast ring‐closure reaction was even further enhanced.
The World Needs New Colors: Cutting Edge Mobility Focusing on Long Persistent Luminescence Materials
Authors: Arras Janet , Bräse Stefan
Published: December 2017

The increasing number of “self‐driving vehicles” produced by the automotive and non‐automotive industries and the increased use of driver assistance systems requires ultimately an adaption of appropriate road markings. For this purpose, carefully designed near‐infrared (NIR) and short‐wave infrared (SWIR) emitters will play an emerging role in the future. Correspondingly this Minireview will present new trends for the application of long persistent luminescence materials for future developments in the field of NIR and SWIR emitters, respectively.
ICCS/ESCCA Consensus Guidelines to detect GPI‐deficient cells in Paroxysmal Nocturnal Hemoglobinuria (PNH) and related Disorders Part 4 – Assay Validation and Quality Assurance
Authors: Oldaker Teri , Whitby Liam , Saber Maryam , Holden Jeannine , Wallace Paul K , Litwin Virginia
Published: December 2017

Over the past six years, a diverse group of stakeholders have put forth recommendations regarding the analytical validation of flow cytometric methods and described in detail the differences between cell‐based and traditional soluble analyte assay validations. This manuscript is based on these general recommendations as well as the published experience of experts in the area of PNH testing. The goal is to provide practical assay‐specific guidelines for the validation of high‐sensitivity flow cytometric PNH assays. Examples of the reports and validation data described herein are provided in Supporting Information. © 2017 International Clinical Cytometry Society
Analysis of instantaneous availability of communication system based on the influence of support equipment
Authors: Yang Yi , Chen Yang , Wen Meilin
Published: December 2017

Taking into account the influence of support equipment, in this paper, we propose an instantaneous availability (IA) model based on the Markov process and queuing theory. Using big data technique, we analyze the massive data of a communication system and generate its main features. We propose a new method to design system, by using these features in the proposed IA model. Two typical fault modes in communication system are studied. Firstly, an IA model considering repair equipment failure in the maintenance of one electronic unit is proposed. Then, we further enhance the IA model by exploring the queuing problem of multiple electronic units. M/G/1 queuing system is used to analyze the distribution function of waiting and service time. Simulations are performed to illustrate the validity of the model when parameters are under exponential distribution. In addition, we investigate the effect of parameters on IA. As a case study, we analyze the proposed IA model on an optical fiber transmission system and show the validity and applicability of the model.
“Keeping it on your radar”—assessing the barriers and facilitators to a timely diagnosis of type 1 diabetes in childhood: A qualitative study from the early detection of type 1 diabetes in youth study
Authors: Townson Julia , Gallagher Dunla , Cowley Laura , Channon Susan , Robling Michael , Williams David , Hughes Clare , Murphy Simon , Lowes Lesley , Gregory John W.
Published: December 2017

Aims

The aim of this study was to explore from the perspectives of key stakeholders involved in the pathway to diagnosis, the barriers and facilitators to a timely diagnosis of type 1 diabetes in childhood.

Methods

Qualitative interviews and free‐text analyses were undertaken in 21 parents with a child diagnosed with type 1 diabetes, 60 parents without a child diagnosed with type 1 diabetes, 9 primary healthcare professionals, 9 teachers and 3 community diabetes liaison nurses. Data were analysed thematically and 30% double coded.

Results

Two key themes were identified, namely the importance of widespread awareness and knowledge and seeking healthcare professional help. Parents with a child diagnosed with type 1 diabetes described seeking opinions from a number of individuals prior to seeking health professional help. Healthcare professionals recognized the rarity of the condition and the need for it to be kept on their “radar”, to ensure they considered it when examining an unwell child. The process of obtaining a primary healthcare appointment was identified as potentially playing a crucial role in the diagnostic process. However, most parents with a child diagnosed with type 1 diabetes described receiving an appointment on the day they sought it.

Conclusions

Knowledge and awareness of type 1 diabetes in childhood remain limited in the general population and misconceptions persist relating to how children present with this serious condition. An effective community‐based intervention to raise awareness amongst key stakeholders is required to ensure children receive a timely diagnosis once symptomatic.
Proteomic diversity of high‐density lipoprotein explains its association with clinical outcome in patients with heart failure
Authors: Emmens Johanna Elisabeth , Jones Donald J.L. , Cao Thong H. , Chan Daniel C.S. , Romaine Simon P.R. , Quinn Paulene A. , Anker Stefan D. , Cleland John G. , Dickstein Kenneth , Filippatos Gerasimos , Hillege Hans L. , Lang Chim C. , Ponikowski Piotr , Samani Nilesh J. , van Veldhuisen Dirk J. , Zannad Faiz , Zwinderman Aeilko H. , Metra Marco , de Boer Rudolf A. , Voors Adriaan A. , Ng Leong L.
Published: December 2017

Aims

Previously, low high‐density lipoprotein (HDL) cholesterol was found to be one of the strongest predictors of mortality and/or heart failure (HF) hospitalisation in patients with HF. We therefore performed in‐depth investigation of the multifunctional HDL proteome to reveal underlying pathophysiological mechanisms explaining the association between HDL and clinical outcome.

Methods and results

We selected a cohort of 90 HF patients with 1:1 cardiovascular death/survivor ratio from BIOSTAT‐CHF. A novel optimised protocol for selective enrichment of lipoproteins was used to prepare plasma. Enriched lipoprotein content of samples was analysed using high resolution nanoscale liquid chromatography‐mass spectrometry‐based proteomics, utilising a label free approach. Within the HDL proteome, 49 proteins significantly differed between deaths and survivors. An optimised model of 12 proteins predicted death with 76% accuracy (Nagelkerke R2=0.37, P < 0.001). The strongest contributors to this model were filamin‐A (related to crosslinking of actin filaments) [odds ratio (OR) 0.31, 95% confidence interval (CI) 0.15–0.61, P = 0.001] and pulmonary surfactant‐associated protein B (related to alveolar capillary membrane function) (OR 2.50, 95% CI 1.57–3.98, P < 0.001). The model predicted mortality with an area under the curve of 0.82 (95% CI 0.77–0.87, P < 0.001). Internal cross validation resulted in 73.3 ± 7.2% accuracy.

Conclusion

This study shows marked differences in composition of the HDL proteome between HF survivors and deaths. The strongest differences were seen in proteins reflecting crosslinking of actin filaments and alveolar capillary membrane function, posing potential pathophysiological mechanisms underlying the association between HDL and clinical outcome in HF.
Antiferromagnetic Interactions in Copper(II) µ‐Oxalato Dinuclear Complexes: The Role of the Counterion
Authors: Julve Miguel , Gleizes Alain , Chamoreau Lise Marie , Ruiz Eliseo , Verdaguer Michel
Published: December 2017

We report the preparation, crystal structure determination, magnetic properties and DFT calculations of five oxalato‐bridged dicopper(II) complexes of formula [Cu2(bpy)2(H2O)2(C2O4)](CF3SO3)2 (1), [Cu2(bpy)2(C2O4)](PF6)2 (2), [Cu2(bpy)2(C2O4)](ClO4)2 (3), [Cu2(bpy)2Cl2(C2O4)]·H2O (4) and [Cu2(bpy)2(NO2)2(C2O4)] (5) (bpy = 2,2′‐bipyridine and C2O42– = oxalate). Compounds 1, 2, 4 and 5 crystallize in the monoclinic system and 3 crystallizes in the triclinic system. The oxalate ligands in 1–5 adopt the bis‐bidentate coordination mode and the two bpy molecules act as terminal ligands. The coordination of the counterions and the surroundings of the copper(II) ions differentiate the five compounds. The four nearest neighbours of copper(II) in 1–4 are roughly in the plane of the CuC2O4Cu framework, whereas they are in an almost perpendicular plane in 5. Using the isotropic Hamiltonian H = –J S1·S2, where S1 and S2 are the spin quantum operators for Cu1 and Cu2; J is –384 cm–1 for 1, –392 cm–1 for 2 and –387 cm–1 for 3, slightly decreasing to –328 cm–1 for 4 and falling to –14 cm–1 for 5. The influence of the anions on the magnetic properties of this family of compounds is explained by the changes in the overlap of the magnetic orbitals through the oxalate bridge. DFT calculations reproduce well the experimental values of J and provide an illustration of the magnetic orbitals.
Oligomeric Composition of Palm Olein‐Based Polyols: The Effect of Nucleophiles
Authors: Tuan Ismail Tuan Noor Maznee , Ibrahim Nor Azowa , Mohd Noor Mohd Azmil , Hoong Seng Soi , Poo Palam Kosheela Devi , Yeong Shoot Kian , Idris Zainab , Sendijarevic Christi M. Schiffman Ibrahim , Abd Malek Emilia , Zainuddin Norhazlin , Sendijarevic Vahid
Published: December 2017

Increasing environmental concerns have led to significant breakthroughs in developing vegetable oil‐based polyols, including palm olein‐based polyols (POoPs). The effect of nucleophiles (water, monol, linear, and branched diols) on oligomeric compositions and properties of polyols derived from epoxidized palm olein (EPOo) is investigated. Conversions of EPOo to POoPs are confirmed by FTIR analysis, oxirane oxygen content, and hydroxyl number measurements. GPC calibrated against polyether polyols is used to determine the formation of oligomers of the polyols. Functionalities of POoPs prepared with linear diols are higher than the branched diol determined using GPC and VPO. Lower degree of oligomerization is observed in polyols prepared with water and methanol compared to polyols made with diols. POoPs prepared using water, methanol and 1,2‐propanediol (PG) produces 100% secondary hydroxyls polyols, while reaction with linear diols, polyols with mixture of primary and secondary hydroxyls in the range of 26–36% and 64–74%, respectively are produced. Viscosity and glass transition temperature of POoP PDO, prepared from 1,3‐propanediol (PDO) are higher than POoP PG, prepared from PG, 7789 mPa.s and −15.2 °C compared to 3649 mPa.s and −20.8 °C, respectively.

Practical Application: The POoPs described in this study, that is, polyols from epoxidized palm olein ring‐opened with water, methanol, 1,2‐ethanediol (EG), 1,2‐propanediol (PG), 1,3‐propanediol (PDO), 1,4‐butanediol (BDO), 1,5‐pentanediol (PTDO), and 1,6‐hexanediol (HDO), provide selection of a wider range of vegetable oil‐based polyols for development of partially biobased polyurethane products such as binders, elastomers, and flexible foams.

GPC chromatograms of oligomeric compositions of palm olein‐based polyols.
Synthesis and Unusual NMR‐Spectroscopic Behavior of a Strained Bicyclic Ammonium Salt
Authors: Pusch Stefan , Schollmeyer Dieter , Opatz Till
Published: December 2017

The first synthesis of a 2‐azabicyclo[2.2.0]hexenium salt is described. It is available from pyridine in four steps. This strained bicyclic ammonium salt was characterized by 1H, 13C, and 2D NMR spectroscopy as well as by XRD. Due to its unusual NMR spectroscopic characteristics, DFT calculations were performed to additionally support the proposed structure. The strained cation shows significant hyperconjugative stabilization.
Insights into the uptake, metabolization, and translocation of four non‐steroidal anti‐inflammatory drugs in cress (Lepidium sativum) by HPLC‐MS2
Authors: Emhofer Lisa , Himmelsbach Markus , Buchberger Wolfgang , Klampfl Christian W.
Published: December 2017

The metabolization of four non‐steroidal anti‐inflammatory drugs by cress (Lepidium sativum) was investigated using a HPLC‐MS2 method. Cress was grown hydroponically in water containing 0.1 mg/L of each drug for investigations on the kinetics of drug uptake and metabolization over a growing period of 12 days. It could be shown that the parent drugs are metabolized and the abundance of both the parent drug and the metabolites formed, varies over time. Furthermore the distribution of the investigated substances within the different plant parts changed throughout the duration of the experiment due to translocation. Finally cress was cultivated in a solution containing the four drugs in concentrations as low as 0.001 mg/L to resemble the situation in real reclaimed wastewaters. Employing a QuEChERS approach for sample extraction and HPLC‐MS2 in the multiple reaction monitoring mode allowed detecting nine metabolites in this cress sample.
Compressed Air Energy Storage Models for Energy Arbitrage and Ancillary Services: Comparison Using Mixed Integer Programming Optimization with Market Data from the Irish Power System
Authors: Nikolakakis Thomas , Fthenakis Vasilis
Published: December 2017

A mixed integer linear programming (MIP) model is developed to simulate the dynamic performance of compressed air energy storage (CAES) systems in electricity grids composed of thermoelectric and wind energy generators. The model is termed thermo‐economic (TE) as it uses power curves from CAES manufacturers to simulate the effect of cavern pressure on the operation limits of the compressor and the expander of CAES plants. Here, the TE model and the fixed efficiency (FE) model are tested in a study of the economic potential of CAES for arbitrage and ancillary services in the Irish power system. The two models are compared by simulating the technical and economic performance of CAES under deregulated market conditions. Data from the Irish power system are used and both models are applied to various system specifications and market scenarios, while optimizing the operation of CAES for provision of energy arbitrage and ancillary services. The results show that the TE model returns 15 % to 30 % less profits than the FE one, thus demonstrating that FE models overestimate CAES profitability. This study shows that arbitrage using CAES may not be profitable with current prices in Ireland. However, CAES operation would become profitable if financial mechanisms that capture the important system‐wide benefits of CAES are put in place.
Redox Behavior of a Copper‐Based Methanol Reformer for Fuel Cell Applications
Authors: Papavasiliou Joan , Słowik Grzegorz , Avgouropoulos George
Published: December 2017

Remarkable cycling performance and operation during steam reforming of methanol at 210 °C can be obtained with a CuZnAlOx catalyst supported on the gas diffusion layer of a carbon paper incorporated into the fuel cell anode compartment. Exceptional stability is obtained for at least 100 h under reaction conditions, whereas 10–15 % deactivation is obtained afterwards, in accordance with typical behavior for copper‐based catalysts. Despite that most catalysts of this type suffer from pyrophoricity and sintering phenomena after exposure in air, this is not the case in the present work, where the proposed methanol reformer shows high tolerance under repeated on/off cycles. In accordance with in situ characterization under similar conditions, controlled passivation during shut‐down protects the active metallic copper and prevents undesirable sintering.
Frequency‐dependent principal component analysis of multicomponent earthquake ground motions
Authors: Das Sandip , Hazra Budhaditya
Published: December 2017

Stochastic ground motion simulation techniques are becoming increasingly popular because of enhanced computation power enabling direct simulation of complex response quantities. Priestley process assumption is the most general approach for stochastic modeling of earthquake ground motion. However, a framework for multicomponent ground motion simulation using the general Priestley process assumption is not available. Multicomponent motions are useful especially when the correlation structure between them significantly influences the response. The present study proposes a framework for frequency‐dependent principal component analysis (PCA), which facilitates Priestley process–based simulation of multicomponent ground motions. The study focuses only on the frequency‐dependent PCA part, and the results show high dependency of the principal components/directions on the frequency bands of the signals. The present work also advocates that the frequency‐dependent PCA should be preferred to the conventional PCA as the former can address the issues related to the frequency‐independent uniform modulation associated with the latter.
Glacial curvilineations found along the southern sector of the Laurentide Ice sheet and a hypothesis of formation involving subglacial slope failure in tunnel valleys and subglacial lakes
Authors: Clark Chris D. , Livingstone Stephen J.
Published: December 2017

First discovered in Poland, glacial curvilineations (GCLs) are enigmatic landforms comprising parallel sets of sinuous ridges and troughs of metres amplitude and around 150 m wavelength, found within kilometres‐wide valleys interpreted as being produced by meltwater flowing subglacially. Their morphological and sedimentary characteristics and association with tunnel valleys has been described for some prominent Polish examples. From these observations the existing hypothesis is that they form as a consequence of erosion by longitudinal vortices that develop in subglacial floods. Here we report, for the first time, GCLs found along the southern sector of the Laurentide Ice Sheet in three northern states of the USA. Using mapping and topographic analysis from high resolution digital elevation models we report observations on their morphological properties and landform associations. We find aspects of their context and morphology difficult to explain using the existing hypothesis. We instead suggest that these glacial curvilineations are produced by subglacial bank and slope failures that locally widen tunnel valleys, or that occur near subglacial lake shorelines. Further investigation is required to test this hypothesis and to ascertain the mechanisms of proposed mass movements, which may have occurred by rotational or translational slope failure or by creep deformation. Our preferred mechanism is that such movements occurred where subglacial water was emplaced over previously perma‐frozen ground. Under such circumstances, sediment blocks thawed by the water may then easily glide over a frozen décollement at low slope angles; analogous to subaerial active‐layer glides in permafrost environments. Permafrost spring sapping may have provided lines of weakness for slope failure. If the requirement for permafrost is found to hold, then GCLs may become an important indicator of the palaeo‐distribution of permafrost. Copyright © 2017 John Wiley & Sons, Ltd.
Introduction to the themed issue: Wildfire and Geomorphic Systems
Authors: Wohl Ellen
Published: December 2017

Wildfires alter fluxes of water, sediment, solutes, and organic matter in ways that can be transient or persistent. Alterations in material flux then impact geomorphic processes and landforms in a manner that can also be transient or persistent and that can involve complex response. This themed issue includes papers that document distinctive geomorphic responses in the upland and channel components of forested landscapes in southern Europe, northern Australia, and the western United States. Among the themes that emerge from the collected papers are: (i) the importance of ongoing technological developments, including real‐time instrumentation, ground‐based and aerial remote sensing, isotopic ratios, and numerical models of landscape processes, for documenting and predicting fire‐related geomorphic processes; and (ii) the great uncertainties about future landscape change in a global environment of rapidly changing climate and growing human populations that encroach onto remaining wildlands in fire‐susceptible regions. Copyright © 2017 John Wiley & Sons, Ltd.
The mixed gamble of internationalization in family and nonfamily firms: The moderating role of organizational slack
Authors: Alessandri Todd M. , Cerrato Daniele , Eddleston Kimberly A.
Published: December 2017

Research Summary: The unique preferences of family firms may lead to internationalization strategies that differ from those of nonfamily firms. Furthermore, heterogeneity among family firms may lead to variation in internationalization. From the mixed gamble perspective, we examine the internationalization of different types of family firms (weak family owned, strong family owned, and family owned and managed), as well as nonfamily firms, considering how differences in family involvement alter the perceptions of potential gains and losses to socioemotional and financial wealth. We also highlight the varying sensitivities of nonfamily firms and types of family firms to the effects of available and recoverable slack. Our findings underscore differences in internationalization strategies among family and nonfamily firms and demonstrate that slack alters the mixed gamble calculus of internationalization for the different types of firms.

Managerial Summary: Whether family firms internationalize more or less than nonfamily firms is debated. We aim to reconcile this debate by investigating the extent and breadth of internationalization and home region orientation. We propose that inconsistent results regarding family firms’ internationalization are due to their heterogeneity whereby family ownership and management lead to different preferences. Study results support our framework by demonstrating that while nonfamily firms exhibit the highest levels of internationalization, there is much variance among family firms. Additionally, we demonstrate that financial slack further explains differences between family and nonfamily firms. Our study therefore offers a richer understanding of family and nonfamily firms’ internationalization and reveals significant differences among family firms that suggest family owners and managers view the risks of internationalization differently.
Physical neglect during childhood alters white matter connectivity in healthy young males
Authors: Tendolkar Indira , Mårtensson Johan , Kühn Simone , Klumpers Floris , Fernández Guillén
Published: December 2017

Background

Childhood adversity (CA) leads to greater vulnerability for psychopathology by causing structural as well as functional brain abnormalities. Recent findings on gray matter effects point towards the importance of identifying CA outcome as a function of different CA types, varying in the dimensions of threat and deprivation. Using diffusion tensor imaging, we investigate whether different forms of CA impact differently on white matter connectivity in a healthy cohort not confounded by other aspects of disease.

Methods

In 120 healthy young males, we assessed different forms of maltreatment during childhood with the Childhood Trauma Questionnaire (CTQ). Fractional anisotropy (FA) and mean diffusivity (MD) images were generated and projected onto a white matter skeleton using tract‐based spatial statistics. Correlational analysis between FA, MD, and CTQ subscores was then performed using voxelwise statistics.

Results

Of all CTQ‐subscores, only physical neglect (PN) predicted a decrease of FA but not MD in the bilateral anterior thalamic radiation around the middle frontal gyrus and the right inferior fronto‐occipital fasciculus, the inferior longitudinal fasciculus, the cingulum and precuneus. Reduced FA in the posterior cingulum was related to the effects of PN during childhood on anxiety levels at trend level.

Conclusions

PN may have severe consequences and should be considered equally important to more active forms of abuse. FA changes, particularly in the cingulum, actually appear to a functional consequence and are linked to trait anxiety, a personality dimension that is suggested to be a transdiagnostic risk factor of affective disorders. Potentially this reveals a mechanistic chain that forms one pathyway from CA to disease.
Through your eyes or mine? The neural correlates of mental state recognition in Huntington's disease
Authors: Eddy Clare M. , Rickards Hugh E. , Hansen Peter C.
Published: December 2017

Huntington's disease (HD) can impair social cognition. This study investigated whether patients with HD exhibit neural differences to healthy controls when they are considering mental and physical states relating to the static expressions of human eyes. Thirty‐two patients with HD and 28 age‐matched controls were scanned with fMRI during two versions of the Reading the Mind in the Eyes Task: The standard version requiring mental state judgments, and a comparison version requiring judgments about age. HD was associated with behavioral deficits on only the mental state eyes task. Contrasting the two versions of the eyes task (mental state > age judgment) revealed hypoactivation within left middle frontal gyrus and supramarginal gyrus in HD. Subgroup analyses comparing premanifest HD patients to age‐matched controls revealed reduced activity in right supramarginal gyrus and increased activity in anterior cingulate during mental state recognition in these patients, while manifest HD was associated with hypoactivity in left insula and left supramarginal gyrus. When controlling for the effects of healthy aging, manifest patients exhibited declining activation within areas including right temporal pole. Our findings provide compelling evidence for a selective impairment of internal emotional status when patients with HD appraise facial features in order to make social judgements. Differential activity in temporal and anterior cingulate cortices may suggest that poor emotion regulation and emotional egocentricity underlie impaired mental state recognition in premanifest patients, while more extensive mental state recognition impairments in manifest disease reflect dysfunction in neural substrates underlying executive functions, and the experience and interpretation of emotion.