bluuebunny/crossref_metadata_2025_split huggingface dataset:
Use of LC–HRMS in full scan‐XIC mode for multi‐analyte urine drug testing – a step towards a ‘black‐box’ solution?
Authors: Stephanson N. N. , Signell P. , Helander A. , Beck O. 
Published: May 2017

The influx of new psychoactive substances (NPS) has created a need for improved methods for drug testing in toxicology laboratories. The aim of this work was to design, validate and apply a multi‐analyte liquid chromatography–high‐resolution mass spectrometry (LC–HRMS) method for screening of 148 target analytes belonging to the NPS class, plant alkaloids and new psychoactive therapeutic drugs. The analytical method used a fivefold dilution of urine with nine deuterated internal standards and injection of 2 μl. The LC system involved a 2.0 μm 100 × 2.0 mm YMC‐UltraHT Hydrosphere‐C18 column and gradient elution with a flow rate of 0.5 ml/min and a total analysis time of 6.0 min. Solvent A consisted of 10 mmol/l ammonium formate and 0.005% formic acid, pH 4.8, and Solvent B was methanol with 10 mmol/l ammonium formate and 0.005% formic acid. The HRMS (Q Exactive, Thermo Scientific) used a heated electrospray interface and was operated in positive mode with 70 000 resolution. The scan range was 100–650 Da, and data for extracted ion chromatograms used ± 10 ppm tolerance. Product ion monitoring was applied for confirmation analysis and for some selected analytes also for screening. Method validation demonstrated limited influence from urine matrix, linear response within the measuring range (typically 0.1–1.0 μg/ml) and acceptable imprecision in quantification (CV <15%). A few analytes were found to be unstable in urine upon storage. The method was successfully applied for routine drug testing of 17 936 unknown samples, of which 2715 (15%) contained 52 of the 148 analytes. It is concluded that the method design based on simple dilution of urine and using LC–HRMS in extracted ion chromatogram mode may offer an analytical system for urine drug testing that fulfils the requirement of a ‘black box’ solution and can replace immunochemical screening applied on autoanalyzers. Copyright © 2017 John Wiley & Sons, Ltd.
Micro‐Raman analysis on the combined use of ammonium oxalate and ammonium phosphate for the consolidation and protection of carbonate stone artifacts
Authors: Osticioli Iacopo , Botticelli Guido , Matteini Paolo , Siano Salvatore , Pini Roberto , Matteini Mauro 
Published: May 2017

Ammonium oxalate ((NH4)2C2O4, AmOx) and more recently di‐ammonium phosphate ((NH4)2HPO4, DAP) are used as inorganic agents in the conservation of cultural heritage for protection and consolidation of carbonate stone artifacts. In this work, we carry out a Raman investigation on the extent of penetration provided by a combined use of them. In particular, AmOx followed by DAP, DAP followed by AmOx, and a DAP + AmOx mixture are applied on tablets of pure CaCO3as well as on degraded marble samples. Then, cross‐sections of samples are analyzed in depth from surface to bulk. Characteristic differences in penetration depth of these agents and distribution of their products of interaction with the substrate are detected and discussed. A homogeneous distribution of whewellite inside the substrates down to a depth of ~1 mm was detected, which became larger in highly degraded regions of marble substrate. Ca‐phosphates in the form of hydroxyapatite were detected at greater depth (down to 2.5 mm), confirming better consolidating properties of DAP with respect of AmOx. Among the application methods tested in our investigation, the DAP followed by AmOx treatment appears the most effective. The discussion of results takes into consideration several aspects including solubility and interaction dynamics between reaction products as well as the peculiar morphological features of the artifact, which are evidenced to play a significant role in treatment choice. Copyright © 2017 John Wiley & Sons, Ltd.
Vibrational investigation of pressure‐ and temperature‐induced phase transitions in metal formates templated by ethylammonium ions
Authors: Ciupa Aneta , Ptak Maciej , Mączka Mirosław , da Silva Filho José Gadelha , Freire Paulo Tarso Cavalcante 
Published: May 2017

We report for the first time phonon properties of [CH3CH2NH3][Mg(HCOO)3] (EtAMg). The studied compound undergoes two structural temperature‐induced phase transitions and temperature‐dependent Raman and infrared studies let us to obtain insight into mechanism of these transitions. In particular, very large broadening of infrared and Raman bands, attributed to vibrations of the NH3 groups, revealed highly dynamic nature of these groups in the both high‐temperature phases. This result indicates that the phase transitions at 374 and 426 K are associated with disordering of the template cations. Raman and infrared data also show that both phase transitions are accompanied by significant distortion of the anionic framework. We also present the pressure‐dependent Raman data of EtAMn framework up to 7.1 GPa. These data revealed presence of two pressure‐induced phase transitions, one between 3.7 and 4.0 GPa and second between 5.6 and 6.0 GPa. We discuss mechanisms of these transitions. Copyright © 2017 John Wiley & Sons, Ltd.
Liquid Crystal Elastomer Actuators from Anisotropic Porous Polymer Template
Authors: Wang Qian , Yu Li , Yu Meina , Zhao Dongyu , Song Ping , Chi Hun , Guo Lin , Yang Huai 
Published: May 2017

Controlling self‐assembly behaviors of liquid crystals is a fundamental issue for designing them as intelligent actuators. Here, anisotropic porous polyvinylidene fluoride film is utilized as a template to induce homogeneous alignment of liquid crystals. The mechanism of liquid crystal alignment induced by anisotropic porous polyvinylidene fluoride film is illustrated based on the relationship between the alignment behavior of liquid crystals and surface microstructure of anisotropic polyvinylidene fluoride film. Liquid crystal elastomer actuators with fast responsiveness, large strain change, and reversible actuation behaviors are achieved by the photopolymerization of liquid crystal monomer in liquid crystal cells coated with anisotropic porous films.
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A proteomic‐based investigation of potential copper‐responsive biomarkers: Proteins, conceptual networks, and metabolic pathways featuring Penicillium janthinellum from a heavy metal‐polluted ecological niche
Authors: Feng Xin , Xu Jian , Liang Yu , Chen Guo‐Li , Fan Xian‐Wei , Li You‐Zhi 
Published: May 2017

AbstractFilamentous fungi‐copper (Cu) interactions are very important in the formation of natural ecosystems and the bioremediation of heavy metal pollution. However, important issues at the proteome level remain unclear. We compared six proteomes from Cu‐resistant wild‐type (WT) Penicillium janthinellum strain GXCR and a Cu‐sensitive mutant (EC‐6) under 0, 0.5, and 3 mmol/L Cu treatments using iTRAQ. A total of 495 known proteins were identified, and the following conclusions were drawn from the results: Cu tolerance depends on ATP generation and supply, which is relevant to glycolysis pathway activity; oxidative phosphorylation, the TCA cycle, gluconeogenesis, fatty acid synthesis, and metabolism are also affected by Cu; high Cu sensitivity is primarily due to an ATP energy deficit; among ATP generation pathways, Cu‐sensitive and Cu‐insensitive metabolic steps exist; gluconeogenesis pathway is crucial to the survival of fungi in Cu‐containing and sugar‐scarce environments; fungi change their proteomes via two routes (from ATP, ATP‐dependent RNA helicases (ADRHs), and ribosome biogenesis to proteasomes and from ATP, ADRHs to spliceosomes and/or stress‐adapted RNA degradosomes) to cope with changes in Cu concentrations; and unique routes exist through which fungi respond to high environmental Cu. Further, a general diagram of Cu‐responsive paths and a model theory of high Cu are proposed at the proteome level. Our work not only provides the potential protein biomarkers that indicate Cu pollution and targets metabolic steps for engineering Cu‐tolerant fungi during bioremediation but also presents clues for further insight into the heavy metal tolerance mechanisms of other eukaryotes.
A strategy for molecular diagnostics of Fanconi anemia in Brazilian patients
Authors: Pilonetto Daniela V. , Pereira Noemi F. , Bonfim Carmem M. S. , Ribeiro Lisandro L. , Bitencourt Marco A. , Kerkhoven Lianne , Floor Karijn , Ameziane Najim , Joenje Hans , Gille Johan J. P. , Pasquini Ricardo 
Published: May 2017

AbstractBackgroundFanconi anemia (FA) is a predominantly autosomal recessive disease with wide genetic heterogeneity resulting from mutations in several DNA repair pathway genes. To date, 21 genetic subtypes have been identified. We aimed to identify the FA genetic subtypes in the Brazilian population and to develop a strategy for molecular diagnosis applicable to routine clinical use.MethodsWe screened 255 patients from Hospital de Clínicas, Universidade Federal do Paraná for 11 common FA gene mutations. Further analysis by multiplex ligation‐dependent probe amplification (MLPA) for FANCA and Sanger sequencing of all coding exons of FANCA, ‐C, and –G was performed in cases who harbored a single gene mutation.ResultsWe identified biallelic mutations in 128/255 patients (50.2%): 89, 11, and 28 carried FANCA, FANCC, and FANCG mutations, respectively. Of these, 71 harbored homozygous mutations, whereas 57 had compound heterozygous mutations. In 4/57 heterozygous patients, both mutations were identified by the initial screening, in 51/57 additional analyses was required for classification, and in 2/57 the second mutation remained unidentified. We found 52 different mutations of which 22 were novel.ConclusionThe proposed method allowed genetic subtyping of 126/255 (49.4%) patients at a significantly reduced time and cost, which makes molecular diagnosis of FA Brazilian patients feasible.
Quantitative single breath‐hold renal arterial spin labeling imaging at 7T
Authors: Li Xiufeng , Auerbach Edward J. , Van de Moortele Pierre‐Francois , Ugurbil Kamil , Metzger Gregory J. 
Published: May 2017

PurposeTo evaluate the feasibility of quantitative single breath‐hold renal arterial spin labeling (ASL) imaging at 7T.MethodsA single‐shot fast spin echo FAIR (flow‐sensitive alternating inversion recovery) method was used to perform two studies. First, a multi‐delay perfusion study was performed to estimate the spin labeling temporal bolus width achievable with a local transceiver array coil at 7T. Second, with a conservatively defined bolus width, a quantitative perfusion study was performed using the single subtraction approach. To address issues of
inhomogeneity/efficiency and excessive short‐term specific absorption rates, various strategies were used, such as dynamic radiofrequency shimming and optimization.ResultsA conservative temporal bolus width of 600 ms determined from the multi‐delay study was applied for single‐subtraction imaging to measure the renal blood flow in the cortex and medulla: 303 ± 31.8 and 91.3 ± 15.2 (mL/100 g/min), respectively. The estimated spatial and temporal signal‐to‐noise ratios of renal perfusion measurements were 3.8 ± 0.7 and 2.4 ± 0.6 for the cortex, and 2.2 ± 0.6 and 1.4 ± 0.2 for the medulla.ConclusionWith proper management of field strength specific challenges, quantitative renal ASL imaging can be achieved at 7T within a single breath‐hold. Magn Reson Med 79:815–825, 2018. © 2017 International Society for Magnetic Resonance in Medicine.
Patterns of PD‐1, PD‐L1, and PD‐L2 expression in pediatric solid tumors
Authors: Pinto Navin , Park Julie R. , Murphy Erin , Yearley Jennifer , McClanahan Terri , Annamalai Lakshmanan , Hawkins Douglas S. , Rudzinski Erin R. 
Published: May 2017

AbstractBackgroundSignificant antitumor effects have been observed in a variety of malignancies via blockade of immune checkpoints. Interaction of programmed death 1 (PD‐1) with its ligands PD‐L1 and PD‐L2 suppresses T‐cell function and restricts immune‐mediated tumor killing. We examined expression of these proteins in children with solid tumors, as expression may serve as biomarkers of response to this class of drugs.MethodsSections cut from formalin‐fixed paraffin‐embedded (FFPE) tissue blocks were processed and evaluated for PD‐1, PD‐L1, and PD‐L2 by immunohistochemistry (IHC) as well as by mRNA expression. A semiquantitative 0–5 IHC scoring system (0 = negative to 5 = very high) was applied, with scores incorporating combined prevalence of tumor cell and nontumor cell labeling. Expression profiling was performed using the NanoString nCounter™ system. Data analysis was performed using quantile normalization. All quantile‐normalized data underwent subsequent log10 transformation.ResultsOne hundred twenty‐four FFPE blocks were included in the analysis. PD‐1, PD‐L1, and PD‐L2 IHC were not evaluable in 8, 0, and 12 blocks, respectively. PD‐1, PDL‐1, and PDL‐2 expression was negative to moderate by both IHC (range 0–3) and mRNA expression (range 0–2.62). Correlation between IHC score and mRNA expression was poor for all three tested proteins (PD‐1, r2 = 0.06; PDL‐1, r2 = 0.007; and PDL‐2, r2 = 0.15).ConclusionsExpression of PD‐1, PD‐L1, and PD‐L2 is low in pediatric solid tumors. At low levels of expression, IHC score and mRNA expression correlate poorly. Current and planned clinical trials will determine whether this low level of expression predicts limited response to immune checkpoint inhibitors.
Barriers and facilitators to the implementation of mentalization‐based treatment (MBT) for borderline personality disorder
Authors: Bales Dawn L. , Verheul Roel , Hutsebaut Joost 
Published: May 2017

AbstractThere are several evidence‐based treatments for borderline personality disorder, but very little is known about the success or failure of implementation in daily practice. This study aims to investigate the success or failure of newly started mentalization‐based treatment programs, and to explore the barriers and facilitators. The implementation trajectories of seven different mentalization‐based treatment programs in six mental health clinics in the Netherlands were included in a multiple case study combining a qualitative and quantitative design. Semi‐structured interview data were collected from several stakeholders of each program. Narrative reconstructions of each interview were assessed by 12 independent experts. Results showed that several programs struggled to implement their program successfully, leading to discontinuation in three programs. According to the experts, particularly elements at the organizational level (i.e. organizational support) and team level (i.e. leadership) contributed to implementation outcome. These findings have important implications for the translation of guidelines and research findings in daily practice. Copyright © 2017 John Wiley & Sons, Ltd.
Ultra‐performance liquid chromatography/multiple reaction monitoring mass spectrometry quantification of trastuzumab in human serum by selective monitoring of a specific peptide marker from the antibody complementarity‐determining regions
Authors: Russo R. , Rega C. , Caporale A. , Tonon G. , Scaramuzza S. , Selis F. , Ruvo M. , Chambery A. 
Published: May 2017

RationaleBecause of the large molecular weight, the structural complexity and the similarity with endogenous immunoglobulins present in high concentrations, in vivo quantitative studies with therapeutic monoclonal antibodies are particularly challenging. In this work, an UPLC/MRM MS‐based methodology is described for the quantification of trastuzumab in human serum by monitoring a novel specific peptide marker located within its heavy chain Complementarity‐Determining Region (CDR).MethodsFor maximum sensitivity and selectivity, specific transitions of this diagnostic proteotypic peptide were optimized and monitored at m/z 364.1 → 437.3 (quantitation ion) and m/z 364.1 → 358.0 (confirmation ion). As a proof‐of‐concept, the methodology was applied to the determination of trastuzumab in human serum over a clinically relevant range from 0.02 to 200 μg/mL. The methodology has been evaluated in terms of specificity, linearity, accuracy, precision, detection and quantitation limits.ResultsAn excellent linear response has been obtained in the range from 0.036 to 3.6 fmol/μL for the standard peptide and from 0.03 to 285 fmol/μL for the trastuzumab in human serum with typical R2 values of 0.99. The limit of detection (LOD) and limit of quantification (LOQ) are 0.005 fmol/μL and 0.05 fmol/μL, respectively, with mean bias and RSD values of 18% and 1%, respectively, for quality control samples.ConclusionsThe strategy used to set up the UPLC/MRM MS methodology based on monitoring specific peptide markers within CDRs can be potentially applied to the detection and quantification of other humanized or human mAbs in biological fluids. Copyright © 2017 John Wiley & Sons, Ltd.
Physical modelling of pool and weir fishways with rock weirs
Authors: Kupferschmidt C. , Zhu D. Z. 
Published: May 2017

AbstractThe flow characteristics of pool and weir fishways with rock weirs were studied through physical modelling. Detailed flow measurements were obtained using an acoustic Doppler velocimeter to understand how weir geometry, discharge, and bed slope affect flow patterns, velocity, turbulence kinetic energy, turbulence intensity, and Reynolds shear stresses in the fishway. The weir geometries used in this study are similar to those typically used for river restoration projects. The use of a V‐shaped rock weir was found to reduce the mean streamwise velocity in the pools by about 20% but more than double the maximum velocity magnitude. Two stage–discharge relationships were developed using the standard weir equation and a modified discharge coefficient to account for both flow over the weir and orifice flow through the base of the weir. The use of V‐shaped rock weirs has the potential to offer significant advantages in assisting multispecies fish migration. The results of this study can be applied to the hydrotechnical design of pool and weir fishways with rock weirs and for river restoration projects.
Site fidelity and movement of a small‐bodied fish species, the rainbow darter (Etheostoma caeruleum): Implications for environmental effects assessment
Authors: Hicks K. A. , Servos M. R. 
Published: May 2017

AbstractSmall‐bodied fish species are commonly used for the assessment of environmental effects because they are short lived, abundant, and they mature early. Although they are generally considered to be less mobile than larger bodied species, relatively little is known about their movement patterns. In this study, we tagged 3,001 rainbow darters (Etheostoma caeruleum) (≤76 mm) in the upper Grand River of southern Ontario with visible implant alpha tags and elastomers in 3 riffles. Five hundred sixty‐five fish were recaptured over 4 recapture events (including spawning and nonspawning periods) over a spatial extent of 1900 m. The rainbow darter demonstrated high site fidelity having a median movement of 5 m and with 85% staying within the riffle in which they were originally tagged. Most movements occurred during the spawning period, where males moved at a greater frequency and had a tendency to move longer distances (up to 975 m). There was also a bias in the direction of movement, which was dependent on the recapture season. Overall, the high site fidelity of the rainbow darter makes it a candidate, sentinel species for the assessment of environmental effects.
Zn and Cd‐Based Coordination Networks: Highly Selective Naked Eye Sensing of Pyridine
Authors: Das Kuheli , Mendiratta Shruti , Datta Amitabha , Massera Chiara , Beyene Belete B. , Hung Chen‐Hsiung 
Published: May 2017

AbstractTwo new coordination compounds, namely [Zn(Hstp)2(Hbipy)2] (1) and {[Cd9(2‐stp)6(bipy)6(H2O)12]•7H2O}n (2) have been synthesized hydrothermally. Compound 1 is a mononuclear Zn(II) complex which forms a 3‐D supramolecular framework through hydrogen bonding and π⋯π interactions. Compound 2 consists of a 3‐D network comprising five crystallographically distinct Cd(II) centers. Compound 2 can be further described as a 2‐nodal, 4,6‐c net of topological type tck/hcc where the point symbol is {42.52.62}{45.55.65}2. Interestingly, solvent sensing studies reveals that compound 1 is able to selectively sense pyridine and exhibit a prominent color change; therefore it is considered as a promising naked‐eye sensor.
Selective and Direct Hydrogenation of CO2 for the Synthesis of Formic Acid over a Rhodium Hydrotalcite (Rh‐HT) Catalyst
Authors: Maru Minaxi S. , Ram Sanwala , Adwani Jacky H. , Shukla Ram S. 
Published: May 2017

AbstractRhodium hydrotalcite (Rh‐HT), a heterogeneous catalyst was synthesized, characterized and investigated for CO2 hydrogenation. The catalyst was effectual for the CO2 hydrogenation and selective formation of formic acid at a moderate temperature and was efficiently recycled up to 5 times without any significant loss in activity. A TON of 15840 for formic acid was selectively obtained at 50 bar pressure (1:1, p/p, CO2 and H2) and 60 °C temperature in a mixture of methanol:water (5:1 v/v, 60 mL) as a solvent in 24 h with no additional base. The effect of various reaction parameters was investigated for the reaction rate and CO2 conversion. The formic acid formation rate follows the 1st order kinetic trend regarding the catalyst amount and partial pressure. The determined activation parameters from the temperature dependence rate of formic acid were Ea=33.5 ± 2.5 kJmol−1, ΔH#=30.9 ± 2.5 kJmol−1, ΔS#=‐275 ± 5 Jdeg−1mol−1. The presence of water as a solvent together with methanol have effectively enhanced the performance of the catalyst. The mechanistic routes for CO2 hydrogenation to formic acid are proposed and discussed by the kinetic and experimental observations.
Synthesis, Characteristics and Aliphatic Alcohol Sensing Behavior of Poly(m–aminophenol)/Sulfonic Acid‐Functionalized Multi‐Walled Carbon Nanotube Composite
Authors: Verma Sushil K. , Choudhury Arup , Kar Pradip 
Published: May 2017

AbstractThe in‐situ synthesis and characteristics of sulfonic acid group functionalized multi‐walled carbon nanotubes incorporated poly(m‐aminophenol) composite (PmAP/s‐MWCNT) has been investigated. The fabricated nanocomposite film was successfully exploited as aliphatic alcohol vapor sensor material. The amount of s‐MWCNT inside the PmAP matrix was optimized as about 2 wt% in terms of highest average conductivity achieved (3.2 × 10−2 S/cm) for the composites due to induced site‐selective interaction between the conjugated PmAP chain and s‐MWCNT. The functionalization of MWCNT and the interfacial interaction in the nanocomposite was confirmed by spectroscopic analysis. The morphological analysis of the nanocomposite by Field emission scanning electron microscopy and transmission electron microscopy indicated the formation of PmAP layers (thickness ∼200 nm) on the surfaces of s‐MWCNTs. The nanocomposite sensor exhibited distinct features of the response curves and percent response values for different aliphatic alcohols especially for methanol and ethanol, which could be used as a basis for the selective detection of these pollutant vapors.
Synthesis and Desymmetrization of meso‐2,3‐Diphenylpiperazine for Application in Asymmetric Transformations
Authors: Periasamy Mariappan , Edukondalu Athukuri , Ramesh Eagala 
Published: May 2017

AbstractThe meso‐2,3‐diphenylpiperazine was prepared in 86 % yield with 99:1 dr from the readily accessible 5,6‐diphenyl‐2,3‐dihydropyrazine by NaBH4/MeOH reduction. The corresponding diastereomeric amides prepared using (R)‐(‐)‐menthyl chloroformate, after separation, benzylation and hydrolysis gave both isomers of optically active N‐benzyl‐2,3‐diphenylpiperazine samples in up to 94 % ee which after further enrichment using the simple achiral oxalic acid afforded samples of both enatiomers in 99 % ee. Reaction of the chiral optically active N‐benzyl‐2,3‐diphenylpiperazine with terminal alkynes and aldehydes in the presence of ZnCl2 gave the corresponding propargylamines with very high diasterioselectivities (up to 99:1 dr) from which both enantiomers of chiral allenes were obtained in up to 82–86 % ee by reaction with ZnBr2 in toluene at 120 °C.