bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dihydrogen Bonding and Proton Transfer from MH and OH Acids to Group 10 Metal Hydrides [(tBuPCP)MH] [tBuPCP = κ3‐2,6‐(tBu2PCH2)2C6H3; M = Ni, Pd]
Authors: Osipova Elena S. , Belkova Natalia V. , Epstein Lina M. , Filippov Oleg A. , Kirkina Vladislava A. , Titova Ekaterina M. , Rossin Andrea , Peruzzini Maurizio , Shubina Elena S. 
Published: February 2016

AbstractThe interactions of HA acids {indole, fluorinated alcohols, phenols, and [CpW(CO)3H] (2)]} with the title hydrides [(tBuPCP)MH] [M = Ni (1a), Pd (1b)] have been studied by a combination of spectroscopic (variable‐temperature IR, NMR, UV/Vis) and computational (DFT/M06, AIM) methods in THF and toluene. The formation of the dihydrogen bond (DHB) 1···HA is the first step in a process leading to proton transfer and H2 evolution. The DHBs of 1 with 2 are much weaker than those of 1 with NH or OH acids, but the former complexes are more reactive. Kinetic studies of the reactions of 4‐(4′‐nitrophenylazo)phenol and [CpWH(CO)3] with 1b in THF gave activation enthalpies ΔH≠ = 9.2 ± 0.4 and 6.5 ± 1.5 kcal mol–1 and activation entropies ΔS≠ = –30 ± 1 and –35 ± 6 cal mol–1 K–1, respectively. Calculations revealed the (η2‐H2)‐like TS (ΔE≠ = 9.3 kcal mol–1) for the reaction of 1b with p‐nitrophenol and the [Pd(η2‐H2)]+OAr– complex as a local minimum at around 5 kcal mol–1 above the DHB adduct. In the reaction of 1b with 2, both the acidic WH and hydridic NiH or PdH bonds undergo heterolytic cleavage (ΔE≠ = 7.4 kcal mol–1) to yield the unusual µ,η1:1‐H2 end‐on complex. The µ,η1:1‐H2 molecule transforms easily into the more stable η2‐H2 side‐on tautomer, which eventually gives the bimetallic product after H2 evolution.
A rapid in‐house validated GC‐FID method for simultaneous determination of lipophilic bioactives in olive oil: Squalene, α‐tocopherol, and β‐sitosterol
Authors: Seçmeler Özge , Güçlü Üstündağ Özlem 
Published: February 2016

The analytical methodologies utilizing HPLC or GC techniques for the determination of predominant lipophilic bioactives in olive oil (β‐sitosterol, squalene, and α‐tocopherol) may include a number of sample pre‐treatment steps (such as clean up (using TLC and SPE), saponification, and derivatization) making them rather lengthy and impractical. The objective of this study was to develop a rapid and in‐house validated GC‐FID method for the simultaneous determination of these bioactives using response surface methodology for optimization of critical parameters (time and temperature of saponification and derivatization). In‐house method validation based on method performance parameters (linearity, limit of detection (LOD), limit of quantification (LOQ), repeatability, and recovery) was carried out using optimized method parameters (10 min derivatization time for 30°C derivatization temperature, 56°C saponification temperature, and 10 min saponification time). The linear range of β‐sitosterol, squalene, and α‐tocopherol was determined to be between LOQ value (8.4; 16.0; 12.5 mg/100 g, respectively) and upper end (500; 700 mg/100 g for β‐sitosterol; squalene, respectively) with acceptable accuracy, recovery (92–97%; 93–95%; 93–110%) and repeatability.Practical applications: The in‐house GC‐FID method developed in this study offers a rapid, accurate and validated method alternative to current official methods and simultaneous methods recently published in the literature. Time of analysis was reduced to ∼5 h for every six samples compared to ∼20 h specified in official methods. The developed method was fully validated covering all parameters; linearity, LOQ, LOD, recovery, and repeatability. This method can be incorporated into quality control programs for olive oil and its application areas can be expanded to include other plant oils after further validation studies.A new rapid multicomponent in‐house validated method was developed to determine predominant lipophilics of olive oil.
N‐Rich Fused Heterocyclic Systems: Synthesis, Structure, Optical and Electrochemical Characterization
Authors: Fusco Sandra , Maglione Cira , Velardo Amalia , Piccialli Vincenzo , Liguori Rosalba , Peluso Andrea , Rubino Alfredo , Centore Roberto 
Published: February 2016

AbstractA new class of N‐rich fused heterocyclic compounds containing the triazolo‐triazine moiety was synthesized and studied by cyclic voltammetry, UV/Vis spectroscopy, X‐ray diffraction, and first principle computations. All the compounds show reversible or quasi‐reversible reduction processes, with reduction potentials easily tunable within the class. LUMO energies as low as –3.95 eV have been measured. The UV/Vis spectra show highly structured absorptions, indicative of rigid molecular skeletons. The solid‐state packing is dominated by π–π stacking interactions, which are promoted by weak CAr–H···N interactions, whereas face‐to‐edge contacts (T contacts), typical of many fused hydrocarbons, are largely absent.
Titanium Enolate Chemistry at the Beginning of the 21st Century
Authors: Cież Dariusz , Pałasz Aleksandra , Trzewik Bartosz 
Published: February 2016

AbstractThe aim of the microreview is to summarize the current state of knowledge in the field of titanium enolate chemistry. The authors focus on stereoselective organic syntheses promoted by titanium enolates and analyze developments in the synthetic methodology observed in this area during the last fifteen years.
Social functioning in adulthood: Understanding long‐term outcomes of adolescents with chronic pain/fatigue treated at inpatient rehabilitation programs
Authors: Westendorp T. , Verbunt J.A. , Remerie S.C. , de Blécourt A.C.E. , van Baalen B. , Smeets R.J.E.M. 
Published: February 2016

AbstractBackgroundChronic pain and fatigue are both common complaints in childhood and adolescence and often persist over time. The aim of the study was to investigate whether chronic pain/fatigue persists during adulthood and how former patients function and participate in society as adults.MethodsThis historical cohort study used questionnaires to gather the data. Predictors for social participation in adulthood were also identified. Differences in functioning and health care use between young adults with current pain/fatigue complaints and those without were also discussed.ResultsNinety‐four young adults responded; their mean age was 26.6 years and 91.5% were women. The average time since treatment was 10.2 years. 63.4% reported ongoing or new pain/fatigue complaints. 72.0% had a paid job; of those who worked, 22.1% reported taking sick leave in the past month. 78.7% of them reported having one or more chronic diseases.A higher level of pain/fatigue measured pre‐treatment was identified as a predictor for more impaired social participation in adulthood. Young adults with current pain/fatigue complaints reported more healthcare utilization, lower levels of physical functioning and limitations in daily activities due to physical problems.ConclusionsA considerable number of these young adults still have pain/fatigue complaints in adulthood. More pain/fatigue pre‐treatment during adolescence predict impaired functioning in the work‐educational domain in young adulthood.What does this study add?This study examines the social participation of young adults who suffered from severe chronic pain/fatigue during adolescence.Predictors for social participation are reported, as are the differences between young adults with and without persistent pain/fatigue complaints.
Analgesia by telemedically supported paramedics compared with physician‐administered analgesia: A prospective, interventional, multicentre trial
Authors: Brokmann J.C. , Rossaint R. , Hirsch F. , Beckers S.K. , Czaplik M. , Chowanetz M. , Tamm M. , Bergrath S. 
Published: February 2016

AbstractBackgroundIn German emergency medical services (EMS), the analgesia is restricted to physicians. In this prospective, interventional, multicentre trial, complications with and quality of telemedically delegated analgesia were evaluated.MethodsIf prehospital analgesia was necessary, five telemedically equipped paramedic ambulances from four different districts could consult a telemedicine centre. Analgesics were delegated based on a predefined algorithm. Telemedically assisted cases were compared with local historical regular EMS missions using matched pairs. The primary outcome was the frequency of therapeutic complications (respiratory/circulatory insufficiency, allergic reactions). Secondary outcomes were quality of analgesia (11‐point numerical rating scale, NRS) and the frequency of nausea/vomiting.ResultsAnalgesia was necessary in 106 telemedically assisted missions. In 23 cases, the telemedical procedure was used until an EMS physician arrived. Of the remaining 83 cases, 80 could be matched to comparable controls. Complications did not occur in either the study group or the control group (0 vs. 0; p = N/A). Complete NRS documentation was noted in 65/80 (study group) and 32/80 (control group) cases (p < 0.0001). Adequate initial pain reduction (quality indicator: reduction of NRS ≥ 2 points or NRS < 5 at end of mission) occurred in 61/65 versus 31/32 cases (p = 1.0); NRS reduction during mission was 3.78 ± 2.0 versus 4.38 ± 2.2 points (p = 0.0159). Nausea and vomiting occurred with equal frequency in both groups.ConclusionsTelemedical delegation of analgesics to paramedics was safe and led to a pain reduction superior to the published minimum standard in both groups. The documentation quality was better in the telemedicine group.What does this study add?Little is known about the safety and quality of prehospital analgesia carried out by emergency medical services (EMS). Beside potential quality problems, in some countries meaningful pain reduction is limited by legal regulations that allow only physicians to administer analgesics.This first multicentre prospective trial for telemedically delegated analgesia demonstrates that remote analgesia is possible and safe and retains equivalent analgesic quality compared with that administered by onsite EMS physicians.
Pain‐catastrophizing and fear‐avoidance beliefs as mediators between post‐traumatic stress symptoms and pain following whiplash injury – A prospective cohort study
Authors: Andersen T.E. , Karstoft K‐I. , Brink O. , Elklit A. 
Published: February 2016

AbstractBackgroundKnowledge about the course of recovery after whiplash injury is important. Most valuable is identification of prognostic factors that may be reversed by intervention. The mutual maintenance model outlines how post‐traumatic stress symptoms (PTSS) and pain may be mutually maintained by attention bias, fear, negative affect and avoidance behaviours. In a similar vein, the fear‐avoidance model describes how pain‐catastrophizing (PCS), fear‐avoidance beliefs (FA) and depression may result in persistent pain. These mechanisms still need to be investigated longitudinally in a whiplash cohort.MethodsA longitudinal cohort design was used to assess patients for pain intensity and psychological distress after whiplash injury. Consecutive patients were all contacted within 3 weeks after their whiplash injury (n = 198). Follow‐up questionnaires were sent 3 and 6 months post‐injury. Latent Growth Mixture Modelling was used to identify distinct trajectories of recovery from pain.ResultsFive distinct trajectories were identified. Six months post‐injury, 64.6% could be classified as recovered and 35.4% as non‐recovered. The non‐recovered (the medium stable, high stable and very high stable trajectories) displayed significantly higher levels of PTSS, PCS, FA and depression at all time points compared to the recovered trajectories. Importantly, PCS and FA mediated the effect of PTSS on pain intensity.ConclusionsThe present study adds important knowledge about the development of psychological distress and pain after whiplash injury. The finding, that PCS and FA mediated the effect of PTSS on pain intensity is a novel finding with important implications for prevention and management of whiplash‐associated disorders.What does this study add?The study confirms the mechanisms as outlined in the fear‐avoidance model and the mutual maintenance model.The study adds important knowledge of pain‐catastrophizing and fear‐avoidance beliefs as mediating mechanisms in the effect of post‐traumatic stress on pain intensity. Hence, cognitive behavioural techniques targeting avoidance behaviour and catastrophizing may be beneficial preventing the development of chronic pain.
Resilience moderates the association between chronic pain and depressive symptoms in the elderly
Authors: Bauer H. , Emeny R. T. , Baumert J. , Ladwig K.‐H. 
Published: February 2016

AbstractBackgroundChronic pain is frequent in elderly people and, especially if widespread, associated with poor mental health. We investigated whether a resilient personality protects older adults against the adverse effects of chronic pain.MethodsPain status [no pain, chronic local pain (CLP) and chronic widespread pain (CWP)] was determined using the American College of Rheumatologists' criteria for widespread pain in a cross‐sectional sample of 724 participants aged 68–92 years drawn from the population‐based KORA‐Age study in Southern Germany. Depressive symptoms and resilience were assessed via the scales GDS‐15 and RS‐5. The relation between pain, resilience and depressive symptoms was modelled using logistic and quantile regression.ResultsCLP prevalence and CWP prevalence were 57.5% and 12.3%, respectively. Confounder‐adjusted logistic regression indicated a fourfold risk of depressed mood (GDS‐15 ≥ 5) in CWP, vs. no pain (OR = 4.08, 95% CI 1.90–8.74). However, in quantile regression, the adverse effect of CWP was significantly attenuated by resilience when looking at the GDS‐15 score lower quartile (p = 0.011) and median (p = 0.011). This effect appeared to be mainly driven by participants aged 75–84 years. Confounder adjustment reduced the effect of CLP on depressive symptoms to non‐significance, and effect modification by resilience was undetectable in regression models of CLP.ConclusionsResilience was protective in the association of CWP with depressive symptoms in this analysis. Older adults with CWP may potentially benefit from interventions supporting resilience. Prospective research should investigate the protective role of resilience in the potentially self‐perpetuating relation between chronic pain and depressed affect.What does this study add?The association of chronic widespread pain with depressive symptoms in the elderly population is attenuated by resilience.
Neonatal paracetamol treatment reduces long‐term nociceptive behaviour after neonatal procedural pain in rats
Authors: van den Hoogen N.J. , Tibboel D. , Honig W.M.M. , Hermes D. , Patijn J. , Joosten E.A. 
Published: February 2016

AbstractBackgroundPain from skin penetrating procedures (procedural pain) during infancy in the neonatal intensive care unit (NICU) may result in changes of nociceptive sensitivity in later life. This supports the need for pain management during such vulnerable periods in life. This study, therefore, analyses the short‐ and long‐term consequences of neonatal paracetamol (acetaminophen) treatment on pain behaviour in an experimental rat model of neonatal procedural pain.MethodsA repetitive needle‐prick model was used, in which neonatal rats received four needle pricks into the left hind paw per day from postnatal day 0 to day 7 (P0–P7). Paracetamol (50 mg/kg/day s.c.) was administered daily (P0–P7), and sensitivity to mechanical stimuli was compared with a needle‐prick/saline‐treated group and to a tactile control group. At 8 weeks of age, all animals underwent an ipsilateral paw‐incision, modelling postoperative pain, and the duration of hypersensitivity was assessed.ResultsNeonatal paracetamol administration had no effect upon short‐term mechanical hypersensitivity during the first postnatal week or upon long‐term baseline sensitivity from 3 to 8 weeks. However, neonatal paracetamol administration significantly reduced the postoperative mechanical hypersensitivity in young adults, caused by repetitive needle pricking.ConclusionParacetamol administration during neonatal procedural pain does not alter short‐term or long‐term effects on mechanical sensitivity, but does reduce the duration of increased postoperative mechanical hypersensitivity in a clinically relevant neonatal procedural pain model.What does this study add

Paracetamol can be used safely in neonatal rats.

Neonatal paracetamol treatment had no effect upon short‐term mechanical hypersensitivity during the first postnatal week, nor upon long‐term baseline sensitivity from 3 to 8 weeks.

Paracetamol treatment during the first postnatal week significantly reduced the postoperative mechanical hypersensitivity in young adult rats.
Hairpin Assembly Amplified Electrochemical Biosensor for Highly Sensitive and Specific Detection of DNA
Authors: Zhong Changli , Yang Gang , Wang Nian , Ji Feihu , Zhang Ye , Ding Xiaojuan , Yang Junhong , Zhang Jian 
Published: February 2016

AbstractIn this report, a simple electrochemical biosensor has been developed for highly sensitive and specific detection of DNA based on hairpin assembly amplification. In the presence of target DNA, the biotin‐labelled hairpin H1 is opened by hybridizing with target DNA through complementary sequences. Then the opened hairpin H1 assembles with the hairpin H2 to displace the target DNA, generating H1‐H2 complex. The displaced target DNA could trigger the next cycle of hairpins assembly, resulting in the generation of numerous H1‐H2 complexes. Subsequently, the H1‐H2 complex hybridizes with the capture probe immobilized on the electrode. Finally, the streptavidin alkaline phosphatase (ST‐ALP) binds to biotin in the capture probe‐H1‐H2 complex and catalyzes the substrate α‐naphthol (α‐NP) to produce electrochemical signal. To make a more fascinating hairpin assembly amplification strategy in signal amplification, mismatched base sequences are designed in hairpin H2 to decrease non‐specific binding of the hairpin substrates. The developed biosensor achieves a sensitivity of 20 pM with a linear range from 25 pM to 25 nM, and shows high selectivity toward single‐base mismatch. Thus, the proposed electrochemical biosensor might have the potential for early clinical diagnosis and therapy.
Detection of transience in eroding landscapes
Authors: Mudd Simon M. 
Published: February 2016

AbstractPast variations in climate and tectonics have led to spatially and temporally varying erosion rates across many landscapes. In this contribution I examine methods for detecting and quantifying the nature and timing of transience in eroding landscapes. At a single location, cosmogenic nuclides can detect the instantaneous removal of material or acceleration of erosion rates over millennial timescales using paired nuclides. Detection is possible only if one of the nuclides has a significantly shorter half‐life than the other. Currently, the only practical way of doing this is to use cosmogenicin situcarbon‐14 (14C) alongside a longer lived nuclide, such as beryllium‐10 (10Be). Hillslope information can complement or be used in lieu of cosmogenic information: in soil mantled landscapes, increased erosion rates can be detected for millennia after the increase by comparing relief and ridgetop curvature. This technique will work as long as the final erosion rate is greater than twice the initial rate. On a landscape scale, transience may be detected based upon disequilibria in channel profiles or ridgetops, but transience can be sensitive to the nature of transient forcing. Where forcing is periodic, landscapes display differing behavior if forcing is driven by changes in base level lowering rates versus changes in the efficiency of either channel or hillslope erosion (e.g. driven by climate change). Oscillations in base level lowering lead to basin averaged erosion rates that reflect a long term average erosion rate despite strong spatial heterogeneity in local erosion rates. This averaging is reflected in10Be concentrations in stream sediments. Changes in hillslope sediment transport coefficients can lead to large fluctuations in basin averaged erosion rates, which again are reflected in10Be concentrations. The variability of erosion rates in landscapes where both the sediment transport and channel erodibility coefficients vary is dominated by changes to the hillslope transport coefficient. Copyright © 2016 John Wiley & Sons, Ltd.
Building e‐rater® Scoring Models Using Machine Learning Methods
Authors: Chen Jing , Fife James H. , Bejar Isaac I. , Rupp André A. 
Published: February 2016

AbstractThe e‐rater® automated scoring engine used at Educational Testing Service (ETS) scores the writing quality of essays. In the current practice, e‐rater scores are generated via a multiple linear regression (MLR) model as a linear combination of various features evaluated for each essay and human scores as the outcome variable. This study evaluates alternative scoring models based on several additional machine learning algorithms, including support vector machines (SVM), random forests (RF), and k‐nearest neighbor regression (k‐NN). The results suggest that models based on the SVM algorithm outperform MLR models in predicting human scores. Specifically, SVM‐based models yielded the highest agreement between human and e‐rater scores. Furthermore, compared with MLR, SVM‐based models improved the agreement between human and e‐rater scores at the ends of the score scale. In addition, the high correlation between SVM‐based e‐rater scores with external measures such as examinee's scores on the other parts of the test provided some validity evidence for SVM‐based e‐rater scores. Future research is encouraged to explore the generalizability of these findings.
Chemical composition and the anti‐melanogenic potential of different essential oils
Authors: Fiocco Daniela , Arciuli Marcella , Arena Mattia Pia , Benvenuti Stefania , Gallone Anna 
Published: February 2016

AbstractTyrosinase is the key enzyme of melanogenesis, the process that determines skin and hair pigmentation in mammals. In humans, various pigmentary disorders depend on excessive melanin production and accumulation. Moreover, tyrosinase activity can cause the undesirable browning of plant‐derived food. For such reasons, ongoing researches aim at developing effective melanogenesis inhibitors for medical, cosmetic and food applications. Diverse biological activities have been observed for certain plant essential oils (EOs) and their components. In this study, the EOs from nine different plant species were investigated for their anti‐melanogenic potential. The EOs chemical composition was assessed by gas chromatography‐mass spectrometry (GC‐MS) revealing the presence of some constituents with known tyrosinase inhibitory ability. Most EOs inhibited significantly and dose‐dependently mushroom tyrosinase. Two samples also inhibited the activity of tyrosinase from murine B16 melanoma cells. Our findings indicate that some of the analysed EOs may be promising natural sources for developing novel anti‐melanogenic agents, thus having a good potential in medical, cosmetic and food‐processing industries. Copyright © 2016 John Wiley & Sons, Ltd.