bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hydration of nitriles: an examination in terms of No Barrier Theory
Authors: Guthrie J. Peter , Yim Jacky C.‐H. , Wang Qiang 
Published: November 2013

Nitriles pose an interesting problem to the explanatory powers of organic chemistry because, despite the favorable overall thermodynamics of hydrolysis to the corresponding amides, the reactions are inherently slow. The rate determining step is hydration of the nitrile to give the imidic acid, which quickly tautomerizes to the amide. In terms of Marcus Theory, the intrinsic barriers for acid and base‐catalyzed hydration are higher for nitriles than for amides, which are themselves slow reactions. It is remarkable that hydration of a nitrile, for which the free energy change is close to zero except for polyhaloacetonitriles, is much slower than hydration of an amide, which is energetically unfavorable. This can be explained by No Barrier Theory in terms of the high energetic cost of the geometrical distortions in “one thing at a time” corner species.There are no experimental equilibrium constants for this initial hydration step, so we have determined them computationally. The free energy change for the initial hydration is small; it is the fast and energetically downhill second step, tautomerization to the amide, which makes the overall hydrolysis of nitrile to amide thermodynamically favorable. Very few of the pKa values needed in the acid and base‐catalyzed mechanisms are known, so we used linear free energy relations and treat the parent pKa values as adjustable parameters. This procedure leads to pKa values in accord with expectation based on such data as are available and permits calculation of rate constants in satisfactory agreement with experiment. Copyright © 2013 John Wiley & Sons, Ltd.
Quantitative analysis of γ‐ and δ‐lactones in wines using gas chromatography with selective tandem mass spectrometric detection
Authors: Langen Johannes , Wang Chen‐Yin , Slabizki Petra , Wall Kristina , Schmarr Hans‐Georg 
Published: November 2013

RATIONALEAroma relevant γ‐ and δ‐lactones are important flavor compounds in various foodstuffs. Their quantitative determination is essential for evaluating food sensory properties as well as food authenticity studies.METHODSHigh‐throughput head‐space solid‐phase microextraction as sample preparation, separation by capillary gas chromatography coupled with triple stage quadrupole mass spectrometry has been evaluated as the analytical method.RESULTSMonitoring selected reaction mass fragments allowed sub‐µg/L quantification of γ‐ and δ‐lactones in complex wine matrices.CONCLUSIONSTandem mass spectrometry improves specific detection of γ‐ and δ‐lactones, a prerequisite for reliable quantification at low‐µg/L concentration levels in complex wine matrices. Copyright © 2013 John Wiley & Sons, Ltd.
The influence of growth conditions on strain differentiation within the Lactobacillus acidophilus group using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry profiling
Authors: Šedo Ondrej , Vávrová Andrea , Vad'urová Marta , Tvrzová Ludmila , Zdráhal Zbyněk 
Published: November 2013

RATIONALEMatrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) profiling of bacteria is often used to distinguish isolates beyond the species level, even to the level of individual strains. However, the influence of bacterial growth conditions on the discriminatory power of the method to the strain level has not yet been properly evaluated.METHODSFor the purpose of this study, we used an extraction protocol recommended for clinical laboratories for MALDI‐TOF MS profiling of bacteria. Seventeen closely related strains of the Lactobacillus acidophilus group were cultivated under various growth conditions (growth medium, time, and temperature) and analyzed.RESULTSOut of a total of 327 samples, 80 % were correctly assigned to the species level and 13 % only to the genus level. When using data obtained from strains cultured for lengthy periods (7 days), the identification success rate was reduced due to poor signal quality, whereas with shorter cultivation times there was no influence of growth conditions on the assignment of particular strains to their corresponding species. However, variations in certain cultivation parameters were found to influence identification and differentiation of most of the examined strains. Strain discrimination was frequently found to be dependent on the selection of culture conditions. MALDI‐TOF MS data treatment (strain‐specific peak detection, BioTyper scoring, subtyping, or cluster analysis) also contributed to the discriminatory power of the method.CONCLUSIONSWhen MALDI‐TOF MS profiling of bacteria is used for strain discrimination, the cultivation conditions should be properly optimized and controlled as they significantly contribute to the discriminatory power of the method. Copyright © 2013 John Wiley & Sons, Ltd.
On‐line HfF5−/WF5− separation in an O2‐filled radiofrequency quadrupole gas cell
Authors: Zhao X.‐L. , Eliades J. , Litherland A. E. , Kieser W. E. , Cornett J. , Charles C. R. J. 
Published: November 2013

RATIONALEAn experimental Isobar Separator for Accelerator Mass Spectrometry (ISAMS) instrument has been used to demonstrate an on‐line separation of HfF5− from its isobar WF5−. This is necessary, in addition to sample preparation chemistry, for measuring 182Hf at natural levels by Accelerator Mass Spectrometry (AMS).METHODSThe device utilizes a radiofrequency quadrupole (RFQ) controlled gas cell, wherein anion‐gas reactions at eV energies attenuate the interfering isobars of the analyte molecular anions, leaving HfF5− for AMS analysis. The RFQ also helps to control the multiple scattering resulting from the ion‐gas collisions.RESULTSO2 gas was used in the HfF5−/WF5− separation and WF5− was attenuated by nearly 3 orders of magnitude while maintaining ~75% transmission of HfF5−. It is expected that the transmission and attenuation can be increased by further research.CONCLUSIONSThis result advances the possibility of detecting natural 182Hf when AMS is supplemented with an isobar separator in the injection system. Copyright © 2013 John Wiley & Sons, Ltd.
Femtosecond laser‐induced ionization/dissociation tandem mass spectrometry (fsLID‐MS/MS) of deprotonated phosphopeptide anions
Authors: Smith Scott A. , Kalcic Christine L. , Cui Li , Reid Gavin E. 
Published: November 2013

RATIONALERadical‐directed dissociation techniques provide structural information which is complementary to that from conventional collision‐induced dissociation (CID). The analysis of phosphopeptide anions is warranted due to their relatively acidic character. As femtosecond laser‐induced ionization/dissociation tandem mass spectrometry (fsLID‐MS/MS) is uniquely initiated by field ionization, an investigation is warranted to determine whether fsLID may provide novel analytical utility for phosphopeptide anions.METHODSTwenty‐three synthetic deprotonated phosphopeptide anions were introduced into a three‐dimensional quadrupole ion trap mass spectrometer via electrospray ionization. The ion trap was interfaced with a near‐IR (802 nm) ultrashort‐pulsed (35 fs FWHM) ultrahigh‐powered (peak power ~1014 W/cm2) laser system. Performance comparisons are made with other techniques applied to phosphopeptide anion analysis, including CID, electron detachment dissociation (EDD), negative electron transfer dissociation (NETD), activated electron photodetachment dissociation (activated‐EPD), and ultraviolet photodissociation (UVPD).RESULTSFsLID‐MS/MS of multiply deprotonated phosphopeptide anions provides sequence information via phosphorylation‐intact a/x ions in addition to other sequence ions, satellite ions, and side‐chain losses. Novel fragmentation processes include selective c‐ion formation N‐terminal to Ser/Thr and a phosphorylation‐specific correlation between xn–98 ion abundances and phosphorylation at the nth residue. Sequencing‐quality data required about 30 s of signal averaging. fsLID‐MS/MS of singly deprotonated phosphopeptides did not yield product anions with stable trajectories, despite significant depletion of the precursor.CONCLUSIONSMultiply deprotonated phosphopeptide anions were sequenced via negative‐mode fsLID‐MS/MS, with phosphosite localization facilitated by a/x ion series in addition to diagnostic xn–98 ions. fsLID‐MS/MS is qualitatively competitive with other techniques. Further efficiency enhancements (e.g., implementation on a linear trap or/and higher pulse frequencies) may permit sequence analyses on chromatographic timescales. Copyright © 2013 John Wiley & Sons, Ltd.
Photopolymerizable Synthons from Glycerol Derivatives
Authors: Mhanna Ali , Sadaka Faten , Boni Gilles , Brachais Claire‐Hélène , Brachais Laurent , Couvercelle Jean‐Pierre , Plasseraud Laurent , Lecamp Laurence 
Published: November 2013

AbstractPhotopolymerizable monomers based on monoglycerides were prepared by a convenient two‐step procedure. The first one consists of the synthesis of highly pure monoglycerides by an organocatalyzed solvent‐free route. This process was carried out by condensation of bio‐sourced carboxylic acids (i.e. butyric, decanoic, undecylenic or stearic acids) with glycerol carbonate or glycidol in the presence of a quaternary ammonium salt as a catalyst. The obtained bio‐based monoglycerides were modified in the second step by reaction with acryloyl and methacryloyl chloride leading to a series of new diacrylated and dimethacrylated monomers. The structures of the monoglycerides, diacrylated and dimethacrylated monomers were fully characterized by spectroscopic methods. Photopolymerization investigations monitored by infrared spectroscopy were achieved under ultraviolet radiation in the presence of a photoinitiator. The resulting cross‐linked materials were analyzed by thermal gravimetric analysis, gel content determination and tests of swelling in water, ethanol and methylene chloride. Data relative to the pendulum hardness of these materials are also included.
Becoming a Composer: Walther's Songs inDie Meistersinger
Authors: GROOS ARTHUR 
Published: November 2013

AbstractWalther von Stolzing's songs inDie Meistersinger von Nürnberghave not attracted much critical interest, in part because of their deceptive appearance as straightforward diegetic music or stage songs. But in addition to comprising an extended ‘musical joke’ illustrating the hero's desire-driven progress towards musical competence, these songs also pursue a historicising agenda, replacing the Meistersingers' pre-modern rule-driven poetics of imitation with a modern aesthetics of inspiration.
Study of a geo‐multicast framework for efficient message dissemination at unmanned level crossings
Authors: Ansari Keyvan , Feng Yanming , Singh Jack 
Published: November 2013

Collisions among trains and cars at road/rail level crossings (LXs) can have severe consequences such as high level of fatalities, injuries and significant financial losses. As communication and positioning technologies have significantly advanced, implementing vehicular ad hoc networks (VANETs) in vicinity of unmanned LXs, generally LXs without barriers, is seen as an efficient and effective approach to mitigate or even eliminate collisions without imposing huge infrastructure costs. VANETs necessitate unique communication strategies, in which routing protocols take a prominent part in their scalability and overall performance, through finding optimised routes quickly and with low bandwidth overheads. This article studies a novel geo‐multicast framework that incorporates a set of models for communication, message flow and geo‐determination of endangered vehicles with a reliable receiver‐based geo‐multicast protocol to support cooperative level crossings (CLXs), which provide collision warnings to the endangered motorists facing road/rail LXs without barriers. This framework is designed and studied as part of a $5.5 m Government and industry funded project, entitled ‘Intelligent‐Transport‐Systems to improve safety at road/rail crossings’. Combined simulation and experimental studies of the proposed geo‐multicast framework have demonstrated promising outcomes as cooperative awareness messages provide actionable critical information to endangered drivers who are identified by CLXs.
Selective inhibitor of endosomal trafficking pathways exploited by multiple toxins and viruses
Authors: Gillespie Eugene J. , Ho Chi-Lee C. , Balaji Kavitha , Clemens Daniel L. , Deng Gang , Wang Yao E. , Elsaesser Heidi J. , Tamilselvam Batcha , Gargi Amandeep , Dixon Shandee D. , France Bryan , Chamberlain Brian T. , Blanke Steven R. , Cheng Genhong , de la Torre Juan Carlos , Brooks David G. , Jung Michael E. , Colicelli John , Damoiseaux Robert , Bradley Kenneth A. 
Published: November 2013

Significance
Bacterial and viral infections are a significant public health burden. To corrupt normal host cellular functions, many bacterial toxins and all viruses must gain entry to host cells, a process that exploits the host’s own cellular machinery. In this study, we use high-throughput technologies to screen for chemical inhibitors of bacterial toxin and viral entry. We report the discovery of a small molecule that inhibits several viruses and bacterial toxins. In addition to the therapeutic potential, this compound represents a powerful probe for dissecting the mechanisms of mammalian membrane trafficking processes.
Molecular determinants of PI3Kγ-mediated activation downstream of G-protein–coupled receptors (GPCRs)
Authors: Vadas Oscar , Dbouk Hashem A. , Shymanets Aliaksei , Perisic Olga , Burke John E. , Abi Saab Widian F. , Khalil Bassem D. , Harteneck Christian , Bresnick Anne R. , Nürnberg Bernd , Backer Jonathan M. , Williams Roger L. 
Published: November 2013

Significance
Pathology of many diseases depends on signaling by phosphoinositide 3-kinase gamma (PI3Kγ), the lipid kinase that is exquisitely adapted to activation downstream of heterotrimeric G-protein–coupled receptors (GPCRs). Using hydrogen–deuterium exchange mass spectrometry, we demonstrate the mechanism by which the p110γ catalytic subunit and its p101 regulatory subunit interact with G-protein Gβγ heterodimers liberated upon GPCR activation. We identify residues in both p110γ and p101 interacting with Gβγ heterodimers on membranes. This enabled us to generate Gβγ-insensitive p110γ and p101 variants that eliminate activation of PI3Kγ by Gβγs without affecting the enzyme’s basal activity or its activation by the small G-protein Ras. Ablating the interaction of PI3Kγ with Gβγ heterodimers attenuates signaling, chemotaxis, and transformation driven by a GPCR agonist in cell lines.
Mutually opposing forces during locomotion can eliminate the tradeoff between maneuverability and stability
Authors: Sefati Shahin , Neveln Izaak D. , Roth Eatai , Mitchell Terence R. T. , Snyder James B. , MacIver Malcolm A. , Fortune Eric S. , Cowan Noah J. 
Published: November 2013

Significance
Animals often produce substantial forces in directions that do not directly contribute to movement. For example, running and flying insects produce side-to-side forces as they travel forward. These forces generally “cancel out,” and so their role remains a mystery. Using a multidisciplinary approach, we show that mutually opposing forces can enhance both maneuverability and stability at the same time, although at some energetic cost. In addition to challenging the maneuverability–stability dichotomy within locomotion, our results challenge the same tradeoff within the engineering of mobile robots. This may inspire the exploration of a new set of strategies for the design and control of mobile systems.
Estrogen receptor (ER) β expression in oligodendrocytes is required for attenuation of clinical disease by an ERβ ligand
Authors: Khalaj Anna J. , Yoon JaeHee , Nakai Jaspreet , Winchester Zachary , Moore Spencer M. , Yoo Timothy , Martinez-Torres Leonardo , Kumar Shalini , Itoh Noriko , Tiwari-Woodruff Seema Kaushalya 
Published: November 2013

Significance
Multiple sclerosis (MS) is a debilitating neurodegenerative disease characterized by inflammation and demyelination. Immunomodulatory agents slow, but do not prevent, disease progression and offer only indirect neuroprotection. The estrogen receptor β (ERβ) ligand diarylpropionitrile (DPN) has direct neuroprotective effects in a mouse model of MS by stimulating endogenous myelination. Here we elucidate the cell type(s) mediating DPN’s effects. Conditional knockout of ERβ in oligodendrocyte (OL) lineage cells prevented DPN-induced improvement in clinical disease and myelination, partially prevented callosal conduction improvement, and prevented activation of a pathway implicated in OL survival/axon myelination. Our results indicate that DPN-conferred neuroprotection in a mouse model of MS is mediated by ERβ in OLs and inform highly targeted pharmacotherapeutic approaches to MS treatment.
ADP-ribosyl-acceptor hydrolase 3 regulates poly (ADP-ribose) degradation and cell death during oxidative stress
Authors: Mashimo Masato , Kato Jiro , Moss Joel 
Published: November 2013

Significance
Poly (ADP-ribose) (PAR) participates in initiating parthanatos, cell death mediated by apoptosis-inducing factor (AIF), following genotoxic stress. PAR translocation from the nucleus to cytoplasm is an essential step for AIF-mediated cell death. Here, we report that poly (ADP-ribose) glycohydrolase (PARG) enhances PAR translocation by releasing protein-free PAR fragments from nuclear acceptor proteins. ADP-ribosyl-acceptor hydrolase (ARH) 3 lowers PAR levels in the nucleus and cytoplasm, preventing PAR translocation and then parthanatos. Elucidation of the sequential action of PARG and ARH3 in the PAR-mediated pathway provides a better understanding of mechanisms underlying oxidative stress and may lead to new therapeutic targets.
Regulatory R region of the CFTR chloride channel is a dynamic integrator of phospho-dependent intra- and intermolecular interactions
Authors: Bozoky Zoltan , Krzeminski Mickael , Muhandiram Ranjith , Birtley James R. , Al-Zahrani Ateeq , Thomas Philip J. , Frizzell Raymond A. , Ford Robert C. , Forman-Kay Julie D. 
Published: November 2013

SignificanceIntrinsically disordered proteins lack persistent folded structure but are abundant and critical for regulatory protein interactions. They represent a challenge to the structure/function paradigm, particularly when significant disorder remains on interaction with partners. Although many disordered protein interactions have been described, little is known about multiple interactions of hub proteins or dependence on posttranslational modifications of the interaction network from a biophysical perspective. Cystic fibrosis transmembrane conductance regulator (CFTR), the chloride channel mutated in cystic fibrosis, is controlled by a disordered, phosphorylated regulatory region. Our detailed characterizations of phosphorylation-dependent interactions of the regulatory region and structural models of its highly dynamic complexes provide direct insight into the basis of CFTR regulation and the general binding mechanisms of disordered hub proteins.
Photoswitchable nanoparticles for in vivo cancer chemotherapy
Authors: Tong Rong , Chiang Homer H. , Kohane Daniel S. 
Published: November 2013

Significance
The importance of this research is in the demonstration of the effectiveness and improved safety of a nanoparticulate chemotherapeutic formulation that can be phototriggered to shrink in size at the tumor site. That shrinkage enhanced nanoparticle penetration into tumors and also triggered local drug release. The result was increased efficacy and reduced systemic toxicity. The phototriggered formulation also relieved the compression of tumor blood vessels, which is a recognized barrier to nanoparticle accumulation in tumors.
Rescue of a primary myelofibrosis model by retinoid-antagonist therapy
Authors: Hong Suk-Hyun , Dvorak-Ewell Melita , Stevens Hazel Y. , Barish Grant D. , Castro Glenda L. , Nofsinger Russell , Frangos John A. , Shoback Dolores , Evans Ronald M. 
Published: November 2013

Significance
Our work identifies a therapeutically tractable yet previously unrecognized repressive epigenetic feature of primary myelofibrosis that controls a key cytokine circuit in the bone marrow microenvironment. Though lacking previous clinical utility, we show that an orally active retinoic acid receptor antagonist can normalize thrombopoietin production, restore bone integrity, and dramatically reduce fibrosis. This identification of a pathway-specific drug for primary myelofibrosis opens up an avenue of treatment options and provides insight into the complex mechanisms underlying myelofibrosis.
Neural mechanisms of reactivation-induced updating that enhance and distort memory
Authors: St. Jacques Peggy L. , Olm Christopher , Schacter Daniel L. 
Published: November 2013

Significance
Reactivation is a key process that updates memory by strengthening existing memories and incorporating relevant new information, thus supporting the dynamic and flexible nature of memory. This adaptive function, however, can sometimes contribute to memory distortions. The current study examines how neural mechanisms that operate during reactivation of memories for a museum tour contribute to enhancement of existing memories, while also supporting integration of novel information that can contribute to false memories. Our results reveal similarities and differences in the neural mechanisms of reactivation associated with subsequent true and false memories for real-world events, thereby illuminating how memories change over time as a consequence of reactivation—a process that has important implications for understanding the unreliability of eyewitness memories.
Broker-dealer e-mail systems must keep pace with firm growth, FINRA says
Authors: A. Nathan Daniel , A. Howes Kelley 
Published: November 2013

Purpose
– The purpose of the paper is to explain the implications of a FINRA disciplinary action and recommend ways for broker-dealers to assess their compliance with supervisory and recordkeeping obligations related to electronic communications.

Design/methodology/approach
– The paper explains supervisory failures related to e-mail retention leading to a FINRA disciplinary action, discusses lessons learned, and recommends best practices that broker-dealers should consider implementing to ensure their systems are consistent with relevant FINRA rules including compliance audits, remediation of identified issues, training, and disciplinary actions.

Findings
– FINRA is clearly signaling that directing firm resources to the building of a business without a similar commitment to compliance will not be tolerated.

Originality/value
– The paper provides expert guidance from experienced financial services lawyers.
FCPA broker-dealer case highlights compliance risks for financial institutions
Authors: Urofsky Philip , Newcomb Danforth 
Published: November 2013

Purpose
– The purpose of this paper is to provide suggestions to the banking and finance sectors on managing FCPA risks in light of a May 2013 FCPA enforcement action against employees of a US broker-dealer.

Design/methodology/approach
– The paper provides details of the May 2013 enforcement action, cites other FCPA enforcement actions in financial services, discusses various types of FCPA risks for financial services firms, lists elements the US and UK governments have considered in evaluating companies' anti-bribery compliance policies and controls, and recommends measures for financial services firms to limit FCPA risks.

Findings
– The early May FCPA enforcement action makes clear that the financial services industry is very much on the radar screen of the US Securities and Exchange Commission and Department of Justice.

Practical implications
– A general response to limiting FCPA risk should include the development of an effective FCPA compliance program and adequate due diligence into potential third-party partners and target companies. Recent industry experience shows the potential protection in careful and comprehensive FCPA risk identification and risk management efforts.

Originality/value
– The paper provides practical guidance from experienced financial services lawyers.