bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractSerum 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

AbstractThirteen 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

AbstractSupported 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

AbstractSol–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

AbstractBiodiesel 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

AbstractSalt 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

AbstractThe 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

AbstractThe 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

AbstractThe 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

AbstractA 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

AbstractBattery 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

AbstractPatients 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

SummaryIneffective 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

AbstractSubstituting 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

BackgroundCompassion‐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.AimsThe 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.MethodIn 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.ResultsStudy 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).ConclusionsCFI 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

AbstractHere 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

AbstractThe 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.
Analysis of instantaneous availability of communication system based on the influence of support equipment
Authors: Yang Yi , Chen Yang , Wen Meilin 
Published: December 2017

SummaryTaking 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.