bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modified Nanocarbons for Catalysis
Authors: Campisciano Vincenzo , Gruttadauria Michelangelo , Giacalone Francesco 
Published: September 2018

AbstractNanocarbons represent useful scaffolds in the preparation of last generation nanostructured catalysts, and their chemical functionalization through covalent or non‐covalent modification is becoming an important tool for introducing well‐distributed anchoring points and, in the meantime, could be the first step toward the assembling of hybrid nanostructured materials with a hierarchical order. In this Review are reported synthesis and catalytic applications of chemically modified nanocarbons such as fullerene, carbon nanotubes, graphene, nanohorns and nanodiamonds in organocatalytic and metal‐based (metal nanoparticles, organometallic complexes) reactions, covering major chemical reactions encompassing, the oxidation of alcohols, aldehydes, olefins, and silanes, hydrogenation reactions of aldehydes, ketones, and alkenes, dehydrogenative coupling of silanes, C−C coupling reactions, epoxidation of alkenes, CO2 fixation into cyclic carbonates, and asymmetric reactions, among others.
Organocopper(III) Compounds with Well‐defined Structures Undergo Reductive Elimination to Form C—C or C–Heteroatom Bonds
Authors: Liu Liang , Xi Zhenfeng 
Published: September 2018

AbstractReductive elimination around Cu(III) atom arises an increasing attention, since this organometallic pathway has been often proposed in a range of Cu‐based reactions. However, due to limited organocopper(III) compounds with well‐defined structures, this elementary reaction still remains an extremely challenging issue. In this review, structurally well‐defined organocopper(III) compounds are mainly divided into three classes based on their ligands: perfluoromethyl Cu(III) compounds, macrocyclic ligand‐based aryl‐Cu(III) compounds, and spiro organocopper(III) compounds chelated by bidentate ligands. The majority of organocopper(III) compounds display the typical square planar geometry. There also exist a few penta‐coordinated organocopper(III) complexes, which share a weak apical Cu‐L bond. In order to form a cis Cu(III)–C and Cu(III)–Nu bonding geometry required for reductive elimination, the re‐arrangement of coordination modes around tetra‐coordinated Cu(III) atoms is necessary. For the aryl‐Cu(III) cationic complexes with one Cu(III)–C bond, the re‐arrangement is triggered by the coordination of the fifth ligand (solvent or nucleophiles), while for the tetra‐carbon‐coordinated organocuprate(III) compounds, the process might be realized via the cleavage of one Cu(III)–C bond by attack of electrophiles. Stoichiometric and catalytic reactions involving well‐defined organocopper(III) compounds to form C—C or C–heteroatom bonds are discussed to support their intermediacy.
Insight into the Role of Additives in Catalytic Synthesis of Cyclohexylamine from Nitrobenzene
Authors: Li Xuefeng , Wang Zhe , Mao Shanjun , Chen Yiqing , Tang Minghui , Li Haoran , Wang Yong 
Published: September 2018

AbstractCyclohexylamine is a versatile intermediate in various chemical industries, which can be expediently synthesized via hydrogenation of aniline or nitrobenzene. However, such processes always suffer from side reactions. Many reports have found that specific additives can suppress the formation of side products, but the mechanism is still not clear. In this work, results suggest that it is the hydroxide ion of alkali metal hydroxides, rather than the cations, which plays a key role in suppressing the side reactions on supported Ru‐based catalysts. With the assistance of LiOH, the selectivity toward cyclohexylamine increased from 85.4% to 100%. Side products, such as dicyclohexylamine, cyclohexanol and N‐isopropyl cyclohexylamine, could no longer be detected. Theoretical calculations further disclosed that addition of alkali metal hydroxides inhibited the dissociation of enamine and decreased the adsorption energy of cyclohexylamine, which might be the reasons for a better selectivity. However, the addition of alkali metal hydroxides reduced the activity of nitrobenzene hydrogenation by unfolding the condensation reaction route. To recover or even further enhance the catalytic performance, a second metal component was introduced and the resultant RuNi/AC exhibited a significant improvement in activity compared with Ru/AC.
Halogenierungen von Kohlenwasserstoffen – Ein Einsatzgebiet für die Spritzentechnik
Authors: Irmer Erhard 
Published: September 2018

AbstractDie in vielen Schulen gut etablierte Spritzentechnik eignet sich nicht nur für Reaktionen unter Beteiligung von Gasen, sondern auch zum Arbeiten mit flüssigen und leicht flüchtigen Substanzen. Ein interessantes Anwendungsgebiet stellt besonders die Halogenierung von Kohlenwasserstoffen, etwa Bromierungen an Alkanen und Alkenen, dar. So können Substitutions‐ und Additionsreaktionen und die Nachweisreaktionen für die Produkte quasi im Mini‐Abzug durch die Schülerinnen und Schüler selbst durchgeführt werden. Im Artikel werden die dafür nötigen Materialien und Grundfertigkeiten sowie eine Reihe von Experimenten vorgestellt, mit dem sich die Thematik der Halogenierung von Kohlenwasserstoffen erarbeiten lässt.
Quantitative Comparison of Proteomes Using SILAC
Authors: Deng Jingjing , Erdjument‐Bromage Hediye , Neubert Thomas A. 
Published: September 2018

AbstractStable isotope labeling by amino acids in cell culture (SILAC) has become very popular as a quantitative proteomic method since it was firstly introduced by Matthias Mann's group in 2002. It is a metabolic labeling strategy in which isotope‐labeled amino acids are metabolically incorporated in vivo into proteins during translation. After natural (light) or heavy amino acid incorporation, differentially labeled samples are mixed immediately after cell lysis and before any further processing, which minimizes quantitative errors caused by handling different samples in parallel. In this unit, we describe protocols for basic duplex SILAC, triplex SILAC for use in nondividing cells such as neurons, and for measuring amounts of newly synthesized proteins. © 2018 by John Wiley & Sons, Inc.
C‐Alkylation of Secondary Alcohols by Primary Alcohols through Manganese‐Catalyzed Double Hydrogen Autotransfer
Authors: El‐Sepelgy Osama , Matador Esteban , Brzozowska Aleksandra , Rueping Magnus 
Published: September 2018

AbstractA new Mn‐catalyzed alkylation of secondary alcohols with non‐activated alcohols is presented. The use of a stable and well‐defined manganese pincer complex, stabilized by a PNN ligand, together with a catalytic amount of base enabled the conversion of renewable alcohol feedstocks to a broad range of higher‐value alcohols in good yields with water as the sole byproduct. The strategy eliminates the need for exogenous and detrimental alkyl halides as well as the use of noble metal catalysts, making the C‐alkylation through double hydrogen autotransfer a highly sustainable and environmentally benign process. Mechanistic investigations support a hydrogen autotransfer mechanism in which a non‐innocent ligand plays a crucial role.
Recent improvements in sports drug testing concerning the initial testing for peptidic drugs (< 2 kDa) – sample preparation, mass spectrometric detection, and data review
Authors: Görgens Christian , Guddat Sven , Thomas Andreas , Thevis Mario 
Published: September 2018

AbstractIn this work, a novel initial testing assay based on liquid chromatography–mass spectrometry is presented, enabling the detection of peptidic drugs and drug candidates (< 2 kDa) prohibited in sports. The assay covers representatives and metabolites of gonadotropin releasing hormone and its analogs (GnRHs), growth hormone secretagogues (GHS), growth hormone releasing peptides (GHRPs), and the Vasopressin‐analog Desmopressin. The general objective of this work was to reduce sample preparation efforts to a minimum while preserving highest possible sensitivity and specificity of the assay, demonstrating limits of detection between 50 and 200 pg/mL. Here, a “dilute‐and‐inject” strategy provides the simplest conceivable sample preparation procedure. Furthermore, the combination of well‐established strategies for the determination of peptides, such as two‐dimensional liquid chromatography, dimethyl sulfoxide (DMSO)‐assisted electrospray ionization, high resolution mass spectrometric detection and a tailored reporter template, which facilitates data review enormously, provides a high‐throughput initial testing assay for lower molecular mass peptidic and peptide‐related analytes.
Identification of the anabolic steroid 6β‐chlorotestosterone in a dietary supplement
Authors: Falconer Travis M. , Flurer Rick A. , Jones Mary B. , Lorenz Lisa M. , Voelker Sarah E. 
Published: September 2018

AbstractCapsules that were labeled to be performance‐enhancing dietary supplements obtained during an investigation were found to contain an unrecognized steroid‐like substance. This compound was isolated by liquid chromatography (LC) fraction collection and characterized using several qualitative analytical techniques, including ultraviolet (UV) spectroscopy, gas chromatography–mass spectrometry (GC–MS), liquid chromatography‐high resolution accurate mass‐mass spectrometry (LC–HRAM–MS), as well as 1H, 13C, and two‐dimensional nuclear magnetic resonance (NMR) spectrometry. This multi‐technique analytical approach was used to identify the designer steroid as 6β‐chloro‐4‐androsten‐17β‐ol‐3‐one (6β‐chlorotestosterone), an analog of testosterone about which little has been published.
An Electrochemical Immunosensor with Graphene‐Oxide‐Ferrocene‐based Nanocomposites for Hepatitis B Surface Antigen Detection
Authors: Zhao Feijun , Bai Yan , Zeng Ruosheng , Cao Liangli , Zhu Jianming , Han Guocheng , Chen Zhencheng 
Published: September 2018

AbstractThe detection of hepatitis B surface antigen (HBsAg), a coat protein secreted by hepatitis B virus, is a common method for confirming infection in early diagnosis. A new composite of graphene oxide‐ferrocene‐chitosan (GO‐Fc‐CS) was synthesized and used to develop an electrochemical immunosensor with a GO‐Fc‐CS/Au‐nanoparticle layer film for HBsAg detection. The modified layer film exhibited not only enhanced electron conductivity, but also strong reversible redox signal for current changes, excellent biocompatibility, and good film‐forming ability for binding a large number of antibodies. The immunosensor exhibits a wide linear range from 0.05 to 150 ng/mL and detection limit of 0.01 ng/mL for HBsAg. The excellent performance in HBsAg detection suggests that the proposed immunosensor has potential application in clinical diagnosis.
Electrochemical Determination of Arsenic Using Silver Nanoparticles
Authors: Sonkoue Baudelaire Matangouo , Tchekwagep Patrick Marcel Seumo , Nanseu‐Njiki Charles Péguy , Ngameni Emmanuel 
Published: September 2018

AbstractIn the present work, silver colloid was produced by chemical reduction of silver salt (silver nitrate) using citrates in aqueous solution. UV‐Vis spectrophotometry indicated the formation of nanoparticles. The surface plasmon resonance peak in absorption spectra of the silver colloidal solution showed an absorption maximum at 435 nm. The dynamic light scattering and zeta potential measurements showed that the size and the zeta potential of the synthesized nanoparticles were about 98 nm and −50 mV respectively. The nanoparticles have been used to modify the gold electrode for use as a potential electrochemical sensor for the analysis of arsenic in aqueous solution. The cyclic voltammogram recorded using gold electrode modified with AgNPs depicted a well‐defined reduction peak of arsenic compared to bare gold electrode. The enhancement of the signal is essentially due to the large surface area attributed to silver nanoparticles. Linear sweep voltammetry has been used to optimize the analytical conditions of arsenic in aqueous solution: it came out that the detection of arsenic in 0.1 M HNO3was optimal while the electrode was conditioned at −0.6 v during 300 s. Under these optimum conditions, a calibration curve was plotted in the concentration range of 0.05 μM to 0.2 μM and the detection limit was estimated at 1.38×10−8 M, calculated from a ratio signal/noise 3.
Hydrogen as a Bio‐Orthogonal Trigger for Spatiotemporally Controlled Caged Prodrug Activation
Authors: Herzog Antoine F. , Schneider Elia M. , Stark Wendelin J. 
Published: September 2018

AbstractThe use of a p‐nitrobenzyloxycarbonyl (pNZ) protecting group on the FDA‐approved lung cancer drug gemcitabine affords a caged drug with very low in vitro toxicity in a human model cell line (A549). To activate this type of caged potent drug, simultaneous presence of two items is needed: platinum nanoparticles and hydrogen‐containing gas mixtures. This combination may later allow a more precise and controlled local delivery of highly potent cytostatic compounds, and may eventually permit reduction of the severe side effects of such chemotherapy treatments. Hydrogen, though an unusual medical agent, is well tolerated, and here used mixtures are derived from diving (deep diving gas). Pt nanoparticles at here used concentrations may eventually be locally deposited into the lungs through minimal invasive inhalation. We demonstrate the use of hydrogen as an on/off uncaging switch and show repeated use of the Pt nanoparticles for a series of uncaging events.
Policy intervention for access to medicine: Does it work similarly for poor and non‐poor?
Authors: Dutta Arijita , Bandyopadhyay Satarupa 
Published: September 2018

SummaryMany federal states in India have recently taken steps to improve distribution and affordability of medicines across public hospitals for reducing high out‐of‐pocket (OOP) expenditure. West Bengal has introduced a Public‐Private Partnership (PPP) scheme, Fair Price Medicine Shops (FPMS) within government hospitals in 2012, which offers high discounts on maximum retail price of the drugs. This model introduces the state as a facilitator, rather than provider or financer, of health care. This paper attempts to measure its impact on OOP expenditure (OOPE) of patients using propensity‐score‐matching technique on the data collected from primary survey among patients. The study finds that although for non‐poor patients, the average OOPE has reduced significantly, the impact has been counter‐productive for the poor patients, hinting that PPP intervention seems to work only for relatively better‐off people, as the best alternative for the poorest remains to be free provision of drugs from the government. The difference in outcome lay in the fact that the nature of control groups differed between poor and non‐poor patients. Those poor patients who did not visit FPMS received most of the medicines free (hence OOPE nearly zero), while for the non‐poor patients not visiting FPMS bought the drugs from outside retail shops.
Attending to gender in psychotherapy: Understanding and incorporating systems of power
Authors: Budge Stephanie L. , Moradi Bonnie 
Published: September 2018

AbstractThis study reviews the research evidence on the effectiveness of attending to clients’ gender identity and gender as a system of power in psychotherapy. We begin with definitions and measures of gender identity and provide clinical examples. Next, we summarize our search for studies to conduct two meta‐analyses on: (a) randomized controlled trials (RCTs) of psychotherapy conducted with transgender clients, and (b) RCTs of the outcomes of psychotherapies that attend explicitly to gender as a system of power compared with another bona‐fide psychotherapy. Our search did not yield studies that fit either search criteria; thus, meta‐analyses were not conducted. Instead, we conducted a content analysis of the 10 qualitative and quantitative studies on psychotherapy with transgender individuals. We conclude by highlighting the limitations of the research base, describing diversity considerations, and recommending therapeutic practices that attend to gender, gendered systems of power, oppression, and privilege.
Engaging in LGBQ+ affirmative psychotherapies with all clients: Defining themes and practices
Authors: Moradi Bonnie , Budge Stephanie L. 
Published: September 2018

AbstractThe clinical need for lesbian, gay, bisexual, and queer (LGBQ+) affirmative psychotherapies has been widely recognized; however, empirical research on the outcomes of such psychotherapies is limited. Moreover, key questions about whom such psychotherapies are for and what they comprise require critical consideration. We begin by offering definitions to answer these questions and delineate four key themes of LGBQ+ affirmative psychotherapies. We conceptualize LGBQ+ affirmative psychotherapies not as sexual orientation group‐specific, but rather as considerations and practices that can be applied with all clients. We then summarize our own search for studies to attempt a meta‐analysis and we discuss limitations and directions for research based on our literature review. We end by delineating diversity considerations and recommending therapeutic practices for advancing LGBQ+ affirmative psychotherapy with clients of all sexual orientations.
Intolerance of uncertainty moderates the relations among religiosity and motives for religion, depression, and social evaluation fears
Authors: Howell Ashley N. , Carleton R. Nicholas , Horswill Samantha C. , Parkerson Holly A. , Weeks Justin W. , Asmundson Gordon J. G. 
Published: September 2018

AbstractObjectivesIntolerance of uncertainty (IU) underlies several psychological disorders, and religion may help some individuals cope with IU and/or protect against psychological symptoms. It was hypothesized that IU would moderate the relations between coping motives for being religious, as well as religiosity, and common psychological disorder symptoms: Depression and social evaluation fears.MethodsStudy 1 included 473 self‐reporting community members (M
age = 48, 48% female, 80% Protestant/Catholic). Study 2 included 412 self‐reporting undergraduates (
M
age = 19, 71% female, 76% Protestant/Catholic).ResultsFor Study 1, coping‐based motives related to greater depression for young adults with above‐average IU and to lower depression for young adults with below‐average IU. For Study 2, religiosity related to lower depression and fear of negative evaluation for individuals with above‐average IU and to greater fear of positive evaluation for individuals with below‐average IU.ConclusionIU may be an important mechanism between aspects of religion and psychological disorder symptoms.
House sparrows (Passer domesticus) adjusted hypothalamic‐pituitary‐adrenal axis negative feedback and perch hopping activities in response to a single repeated stimulus
Authors: Gormally Brenna M. G. , Romero L. Michael 
Published: September 2018

AbstractChronic stress has been extensively studied in both laboratory and field settings; however, a conclusive and consistent phenotype has not been reached. Several studies have reported attenuation of the hypothalamic–pituitary–adrenal axis during experiments intended to cause chronic stress. We sought to determine whether this attenuation could be indicative of habituation. Importantly, we were not investigating habituation to a specific stimulus—as many stress physiology studies do—but rather we assessed how the underlying physiology and behavior changed in response to repeated stressor presentation. We exposed house sparrows (Passer domesticus) to a single stimulus twice per day at random times for 8 consecutive days. We predicted that this period of time would be long enough for the birds to determine that these acute stressors were not, in fact, dangerous and they would, therefore, acclimate. A second control group remained undisturbed for the same period of time. We measured baseline, stress‐induced, negative feedback strength, and maximum production of corticosterone as well as neophobic behavior before, during, and after this 8‐day experiment. When birds experienced a stimulus for 4 days, their negative feedback strength was significantly diminished, but recovered after the second 4 days. Additionally, perch hopping decreased and recovered in this same time frame. These data suggest that distinct physiological and behavioral responses arise when house sparrows are exposed to the same stressor for several consecutive days as opposed to many stressors layered on top of one another. Furthermore, they indicate that habituation—as with chronic stress—can appear differently depending on the metric being examined.
Long‐term griffon vulture population dynamics at Gamla Nature Reserve
Authors: Choresh Yael , Burg David , Trop Tamar , Izhaki Ido , Malkinson Dan 
Published: September 2018

ABSTRACTGamla Nature Reserve (GNR) used to host the largest colony of Eurasian griffon vultures (Gyps fulvus) in northern Israel. Since the early 2000s, the colony has suffered a drastic decline, which could lead to its extinction. In this descriptive study we present the population dynamics at GNR based on an analysis of data collected over 15 years (1999–2013). A monitoring scheme of monthly counts, developed at GNR, provided a database, facilitating a mathematical analysis of the population decline trends and their seasonal fluctuations. The analysis revealed a decline in the population size, which appears similar to an inverse‐sigmoid and indicates a potential extinction of the colony by 2020. The analysis also indicates that, in addition to the overall pattern, the number of vultures fluctuates seasonally, with smaller numbers in spring and greater numbers in autumn and winter. Furthermore, this model suggests that latent factors might have influenced the decline; poisoning, thought to be a root cause, might not be the only factor influencing extinction. We demonstrate the importance of combining frequent data collection with modeling techniques for the analysis of raptor population trends. © 2018 The Wildlife Society.