bluuebunny/crossref_metadata_2025_split huggingface dataset:
Computational study on the recombination reaction between benzyl and propargyl radicals
Authors: Matsugi Akira , Miyoshi Akira 
Published: January 2012

AbstractThe kinetics and mechanisms of the recombination reaction between benzyl and propargyl radicals have been computationally investigated by using the B3LYP, CBS‐QB3, and CASPT2 quantum chemical methods, and the steady‐state unimolecular master equation analysis based on the Rice–Ramsperger–Kassel–Marcus theory. Six distinct recombination channels arising from the radicals' nonequivalent resonance structures (three for benzyl and two for propargyl) were investigated at the CASPT2/cc‐pVTZ//B3LYP/6‐311G(d,p) level, and the respective rate constants were calculated with the variational transition state theory. It was found that the reaction dominantly proceeds by the addition of the propargyl radical to the alpha(CH2) site of the benzyl radical and the additions to the ortho‐ and the para‐sites are unfavorable due to the loss of the aromaticity. The isomerization reaction pathways of the initially formed adducts to methylenecyclopenta‐fused compounds through diradical intermediates were identified. Methylene–indanyl radicals were also identified as products, which are produced by direct H‐atom elimination reactions from the diradical and methylenated indanes. The results of the master equation analyses indicated that the 1‐methylene‐2‐indanyl radical is dominantly produced at high temperature (>1500 K), but the overall rate constant is significantly smaller than the high‐pressure limit within the pressure range studied (0.001–100 atm). The reactions of the triplet biradicals via the intersystem crossing were also suggested to be important and are discussed qualitatively. Investigations on the subsequent reactions of 1‐methylene‐2‐indanyl radicals revealed that the radicals rapidly decompose to 1‐methyleneindene or naphthalene + H. The temperature‐ and pressure‐dependent rate expressions are proposed for kinetic modeling. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 206–218, 2012
Detailed chemical kinetic modeling of JP‐10 (exo‐tetrahydrodicyclopentadiene) high‐temperature oxidation: Exploring the role of biradical species in initial decomposition steps
Authors: Magoon Gregory R. , Aguilera‐Iparraguirre Jorge , Green William H. , Lutz Jesse J. , Piecuch Piotr , Wong Hsi‐Wu , Oluwole Oluwayemisi O. 
Published: January 2012

AbstractThe initial pathways of JP‐10 (exo‐tetrahydrodicyclopentadiene) decomposition are expected to have a significant effect on combustion and pyrolysis behavior of the fuel, affecting, for example, product distribution and ignition delay. Modeling of JP‐10 decomposition should capture these initial decomposition processes as accurately as possible. Two classes of computational approaches have been applied to study intramolecular disproportionation—an important class of reactions in the initial stages of JP‐10 decomposition: (1) the second‐order, multiconfigurational, quasidegenerate perturbation theory employing the complete active space self‐consistent field (CASSCF) reference; and (2) the size‐extensive, left‐eigenstate, completely renormalized (CR) coupled‐cluster (CC) method with singles, doubles, and noniterative triples, termed CR‐CC(2,3), capable of describing reaction pathways involving biradicals. Applying higher levels of theory to points along the CASSCF reaction paths, the barriers to intramolecular disproportionation are much smaller and some barriers appear to vanish. The conventional ring‐opening + disproportionation pathway is compared with an alternative concerted reaction pathway. Overall, this investigation has yielded insights into alkyl disproportionation and ring‐opening reactions that may be of more general use in chemical kinetic modeling. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 179–193, 2012
The enthalpy and entropy of activation for ethyl acetate saponification
Authors: Petek Aljana , Krajnc Majda 
Published: January 2012

AbstractThe saponification of ethyl acetate was measured by conductimetry at different temperatures within a batch reactor. A new mathematical model for obtaining concentration profiles from conductivity was presented and used for reaction‐kinetics' determination. The Arrhenius parameters (A, Ea) showed good agreement with the previously published values. Basic transition‐state theory was used for obtaining the Gibbs energy (ΔG‡), the enthalpy (ΔH‡), and the entropy (ΔS‡) of activation. The low enthalpy of activation and negative entropy of activation were consistent with a reaction pathway when forming a transition‐state complex. The suggested mechanism involves OH−, acting as a general base for removing proton from one of the hydroxide hydrating water, placed directly between it and the ester. The nucleophile from the water then attacks at the electrophilic C of the ester, breaking the π bond, and creating a tetrahedral intermediate. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 692–698, 2012This article was published online on 24 January 2012. An error was subsequently identified. This notice is included in the online and print versions to indicate that both have been corrected on 16 July 2012.
IMPACTS OF LAND COVER CHANGE SCENARIOS ON STORM RUNOFF GENERATION: A BASIS FOR MANAGEMENT OF THE NYANDO BASIN, KENYA
Authors: Olang L. O. , Kundu P. M. , Ouma G. , Fürst J. 
Published: January 2012

ABSTRACTThe effects of conceptual land cover change scenarios on the generation of storm runoffs were evaluated in the Nyando Basin. The spatial scenarios represented alternatives that vary between full deforestation and reforestation. Synthetic storm events of depths 40, 60 and 80 mm were formulated according to the rainfall patterns and assumed to have durations corresponding to the runoff times of concentration. The Natural Resource Conservation Service–Curve Number model was used to generate runoff volumes within the sub‐catchments, which were subsequently routed downstream to obtain effects in the whole basin. The simulated land cover change impacts were evaluated relative to values obtained from the actual land cover state of the basin in the year 2000. From the results, an agricultural land cover scenario constituting of about 86 per cent of agriculture indicated increased runoff volumes in the entire basin by about 12 per cent. An agricultural‐forested land cover scenario with 40 and 51 per cent of forest and agriculture respectively revealed reduced runoff volumes by about 12 per cent. Alternatively, a scenario depicting a largely forested land cover state with about 78 per cent of forests reduced the runoff volumes by about 25 per cent according to the model estimates. Runoff volumes in the basin were also likely to reduce by about 15 per cent if the appropriate land cover scenario for the respective sub‐catchments were to be assumed for runoff management purposes. Considering the prevalent data uncertainty, the study effectively highlights the potential hydrological vulnerability of the basin. The results obtained can form a basis for appropriate catchment management of the area. Copyright © 2012 John Wiley & Sons, Ltd.
Photocoagulation of dermal blood vessels with multiple laser pulses in an in vivo microvascular model
Authors: Jia Wangcun , Tran Nadia , Sun Victor , Marinček Marko , Majaron Boris , Choi Bernard , Nelson J. Stuart 
Published: January 2012

AbstractBackground/ObjectivesCurrent laser therapy of port wine stain (PWS) birthmarks with a single laser pulse (SLP) does not produce complete lesion removal in the majority of patients. To improve PWS therapeutic efficacy, we evaluated the performance of an approach based on multiple laser pulses (MLP) to enhance blood vessel photocoagulation.Study DesignThe hamster dorsal window chamber model was used. Radiant exposure (RE), pulse repetition rate (fr), total number of pulses (np), and length of vessel irradiated were varied. Blood vessels in the window were irradiated with either SLP with RE of 4–7 J/cm2 or MLP with RE per pulse of 1.4–5.0 J/cm2, fr of 0.5–26.0 Hz, and np of 2–5. The laser wavelength was 532 nm and pulse duration was 1 ms. Either a 2 mm vessel segment or entire vessel branch was irradiated. Digital photographs and laser speckle images of the window were recorded before and at specific time points after laser irradiation to monitor laser‐induced blood vessel structural and functional changes, respectively.ResultsWe found that: (1) for a SLP approach, the RE required to induce blood vessel photocoagulation was 7 J/cm2 as compared to only 2 J/cm2 per pulse for the MLP approach; (2) for MLP, two pulses at a repetition rate of 5 Hz and a RE of 3 J/cm2 can induce photocoagulation of more than 80% of irradiated blood vessel; and (3) irradiation of a longer segment of blood vessel resulted in lower reperfusion rate.ConclusionsThe MLP approach can induce blood vessel photocoagulation at much lower RE per pulse as compared to SLP. The 5 Hz fr and the need for two pulses are achievable with modern laser technology, which makes the MLP approach practical in the clinical management of PWS birthmarks. Lasers Surg. Med. 44:144–151, 2012. © 2012 Wiley Periodicals, Inc.
Diagnostic criteria for mild cognitive impairment in Parkinson's disease: Movement Disorder Society Task Force guidelines
Authors: Litvan Irene , Goldman Jennifer G. , Tröster Alexander I. , Schmand Ben A. , Weintraub Daniel , Petersen Ronald C. , Mollenhauer Brit , Adler Charles H. , Marder Karen , Williams‐Gray Caroline H. , Aarsland Dag , Kulisevsky Jaime , Rodriguez‐Oroz Maria C. , Burn David J. , Barker Roger A. , Emre Murat 
Published: January 2012

AbstractMild cognitive impairment is common in nondemented Parkinson's disease (PD) patients and may be a harbinger of dementia. In view of its importance, the Movement Disorder Society commissioned a task force to delineate diagnostic criteria for mild cognitive impairment in PD. The proposed diagnostic criteria are based on a literature review and expert consensus. This article provides guidelines to characterize the clinical syndrome and methods for its diagnosis. The criteria will require validation, and possibly refinement, as additional research improves our understanding of the epidemiology, presentation, neurobiology, assessment, and long‐term course of this clinical syndrome. These diagnostic criteria will support future research efforts to identify at the earliest stage those PD patients at increased risk of progressive cognitive decline and dementia who may benefit from clinical interventions at a predementia stage. © 2012 Movement Disorder Society
Subacute brachial diplegia associated with west nile virus myelitis
Authors: Zafar Sahar F. , Ubogu Eroboghene E. 
Published: January 2012

AbstractIntroduction: Brachial diplegia is a clinical term used to describe weakness restricted to the upper extremities. We report a case of brachial diplegia associated with West Nile virus infection. Methods: A 48‐year‐old man developed severe painless bilateral upper extremity weakness within a few weeks of a flu‐like illness. Results: Clinical examination revealed marked periscapular, shoulder girdle, and humeral muscle atrophy and bilateral scapular winging, with near symmetrical bilateral hypotonic upper extremity weakness. This was associated with clinical signs of an encephalomyelopathy without cognitive or sensory deficits. Electrophysiological studies demonstrated a subacute disorder of motor neurons, their axons or both, involving the cervical and thoracic myotomes, with ongoing denervation. Serological studies confirmed recent West Nile virus (WNV) infection. Gradual improvement occurred following conservative supportive therapies. Conclusions: Progressive brachial diplegia is a rare neuromuscular presentation of WNV neuroinvasive disease. This case report adds to the clinical spectrum of WNV‐induced neurologic sequelae. Muscle Nerve 45: 900‐904, 2012
Unexpected neuroimaging abnormalities in patients with apparent C8 radiculopathy: Broadening the clinical spectrum
Authors: Hehir Michael K. , Figueroa Juan J. , Zynda‐Weiss Andrea M. , Stanton Michael , Logigian Eric L. 
Published: January 2012

AbstractIntroduction: C8‐root impingement by C7/T1 lesions on neuroimaging studies is not consistently observed in C8 radiculopathy. We hypothesized that C7 or T1 root lesions (with a pre‐ or postfixed plexus) or cervical myelopathy might explain some “C8 radiculopathies” without C8 root compression. Methods: Retrospective analysis of cervical neuroimaging in 31 consecutive patients with EMG‐confirmed C8 radiculopathy. Results: Five patients (16%) had C8‐root compression at C7/T1. Of those without C8‐root compression, 5 (16%) had C7‐root compression at C6/7, one (3%) had T1‐root compression at T1/T2, 7 (23%) had cervical cord compression at or above the C6/7 level, 4 (13%) had intramedullary cervical lesions, and 9 (29%) had mild or nonspecific findings. Conclusions: C8 radiculopathy without C8‐root compression may be due to C7‐root compression in the setting of a “prefixed” brachial plexus, upper cervical cord compression with vascular compromise of the distal cervical spinal cord (“myelopathic hand”), or intramedullary cervical cord lesions. Muscle Nerve 45: 859–865, 2012
Reliability of neuromuscular measurements during explosive isometric contractions, with special reference to electromyography normalization techniques
Authors: Buckthorpe Matthew W. , Hannah Ricci , Pain T.G. , Folland Jonathan P. 
Published: January 2012

AbstractIntroduction: This study determined the between‐session reliability of neuromuscular measurements during explosive isometric contractions, with special consideration of electromyography (EMG) normalization. Methods: Following familiarization, 13 men participated in 3 identical measurement sessions involving maximal and explosive voluntary contractions of the knee extensors, while force and surface EMG were recorded. Root mean square EMG amplitude was normalized to different reference measures: (evoked maximal M‐wave peak‐to‐peak amplitude and area, maximum and sub‐maximum voluntary contractions). Results: Explosive voluntary force measurements were reliable on a group level, whereas within‐subject reliability was low over the initial 50 ms and good from 100 ms onward. Normalization of EMG during explosive voluntary contractions, irrespective of the reference method, did not reduce the within‐subject variability, but it did reduce substantially the variability between‐subject. Conclusions: The high intra‐individual variability of EMG and early phase explosive voluntary force production may limit their use to measuring group as opposed to individual responses to an intervention. Muscle Nerve 46: 566–576, 2012
Mechanisms of action of botulinum neurotoxins, β3‐adrenergic receptor agonists, and PDE5 inhibitors in modulating detrusor function in overactive bladders: ICI‐RS 2011
Authors: Kanai Anthony , Zabbarova Irina , Oefelein Michael , Radziszewski Piotr , Ikeda Youko , Andersson Karl‐Erik 
Published: January 2012

AbstractBackgroundBotulinum neurotoxins type A (BoNT/A), β3‐adrenergic receptor agonists, and phosphodiesterase type 5 (PDE5) inhibitors are promising agents that mitigate lower urinary tract symptoms by attenuating the sensory system. However, whether they act directly on afferent nerves or indirectly through the other cell types is unclear.MethodsSpinal cord transected female mice were used as a model for neurogenic bladder overactivity. In vivo methods utilized decerebrate mouse cystometry. In vitro approaches included optical mapping of Ca2+ transient, single unit afferent nerve recordings and tension measurements from bladder sheets and wall cross‐sections. Immunohistochemistry was used to measure the expression of β3‐adrenergic receptors on dorsal root ganglion (DRG) neurons.ResultsOur unique approaches revealed the direct effects of BoNT/A in inhibiting neuropeptide release and firing rates in afferents following bladder injections. β3‐adrenergic receptor agonists are demonstrated to directly inhibit afferent nerve firing independent of the relaxing effects on bladder smooth muscle. Moreover, data suggest the expression of these receptors on DRG neurons that send projections to the bladder. The mechanism of action of PDE5 inhibitors on bladder overactivity is discussed.DiscussionThe questions raised during the plenary session of the 2011 International Consultation on Incontinence‐Research Society meeting regarding the benefits of BoNT/A, β3‐adrenergic receptor agonist and PDE5 inhibitor treatments of overactive bladder are addressed.ConclusionOur findings suggest that the abovementioned agents, in low enough concentrations, can directly inhibit afferent excitability without decreasing detrusor contractility. Accordingly, they have considerable potential for treating the sensory component of lower urinary tract dysfunctions. Neurourol. Urodynam. 31:300–308, 2012. © 2012 Wiley Periodicals, Inc.
Developing a validated urinary diary: Phase 1
Authors: Bright Elizabeth , Cotterill Nikki , Drake Marcus , Abrams Paul 
Published: January 2012

AbstractAimsTo develop and validate a urinary diary, using the psychometric validation protocol applied to all International Consultation on Incontinence Questionnaire (ICIQ) modules.MethodsPatient and clinician opinion was sought on diary content, format, and duration using interviews and questionnaires. Content deemed essential for inclusion were incorporated into four draft diary formats (Phase 1a). Four rounds of content validation using patient‐completed diaries or patient interviews and one round of clinician opinion were undertaken, before a consensus was achieved (Phase 1b).ResultsPhase 1a: 27 patients were interviewed and 30 clinicians returned a questionnaire regarding diary content, format and duration. Content deemed essential for inclusion was identified. Patients reported no format preference but preferred a diary of ≤7 days. Clinicians preferred a 3‐day diary in single sheet format. Phase 1b: 75 of 200 (37.5%) patients returned completed draft diaries. Equal preference for the two portrait format diaries was expressed. Twenty‐six clinicians returned a questionnaire regarding their preference for either of these two options, with 69% (18/26) selecting the one with a printed 24‐hr clock. Optimal diary duration was 4 days. Frequency, voided volume, fluid intake (amount, time and type), time of incontinence episode, and bladder sensation were supported for inclusion in the final diary.ConclusionsDiary content, format, and duration deemed essential by both patients and clinicians have been identified in this preliminary phase, allowing the formation of a draft urinary diary. Further tests of diary validity, reliability and responsiveness will be evaluated in Phase 2 of the study. Neurourol. Urodynam. 31:625–633, 2012. © 2012 Wiley Periodicals, Inc.
COMRADES OR CULPRITS? DONOR ENGAGEMENT AND BUDGET TRANSPARENCY IN AID‐DEPENDENT COUNTRIES
Authors: de Renzio Paolo , Angemi Diego 
Published: January 2012

SUMMARYBudget transparency has come to be considered a key aspect of governance. Over the past decade, donors have invested increasing resources in strengthening processes through which budget transparency in developing countries can be enhanced. According to the 2008 Open Budget Index (OBI) Report, however, aid dependency and budget transparency appear to be inversely correlated. This article looks at the role of donor agencies in promoting or preventing budget transparency in aid‐dependent countries. It looks at significant correlations across the whole sample of 84 countries covered in the 2008 OBI, and analyzes more specific data for a sub‐sample of 16 aid‐dependent countries, before selecting six countries for which more detailed findings are then presented. All of these countries have implemented reforms aimed at enhancing budget transparency, with substantial donor support. These, however, often had only limited success, partly because they were not well adapted to the local context, and partly because donors put limited emphasis on improving public access to budget information. Donor efforts were also often offset by other characteristics of donor interventions, namely their fragmentation, lack of transparency, and limited use of programme aid modalities such as budget support and pooled sector funding. Copyright © 2012 John Wiley & Sons, Ltd.
Indications for antimicrobial prescribing in European nursing homes: results from a point prevalence survey
Authors: Latour Katrien , Catry Boudewijn , Broex Elisabeth , Vankerckhoven Vanessa , Muller Arno , Stroobants Rudi , Goossens Herman , Jans Béatrice ,   On behalf of the European Surveillance of Antimicrobial Consumption Project Group
Published: January 2012

ABSTRACTPurposeIn light of the emerging problem with multiresistant microorganisms in nursing homes (NHs), the European Surveillance of Antimicrobial Consumption NH subproject was set up to measure and describe antimicrobial use across Europe. The aim of this paper was to investigate the indications for antimicrobial use and hence identify targets for quality improvement.MethodsData were obtained from a point prevalence survey conducted in 323 NHs across 21 European countries. A resident questionnaire had to be completed for each resident receiving an antimicrobial, collecting data such as compound name and indication for antimicrobial prescribing. Four main indications for antimicrobial use were recorded: nasal decolonisation of methicillin‐resistant Staphylococcus aureus (MRSA) carriage with mupirocin, prophylactic, empirical, and microbiologically documented treatments. The latter three treatment types were further subdivided according to the targeted infections.ResultsIn total, 1966 residents were treated with 2046 antimicrobials. Empirical treatments were most common (54.4% of all antimicrobial therapies; prevalence: 3.39 per 100 eligible residents), followed by prophylactic (28.8%; prevalence: 1.87%) and microbiologically documented (16.1%; prevalence: 1.01%) regimes. MRSA decolonisation with nasal mupirocin (0.7%; prevalence: 0.02%) was uncommon. Antimicrobials were most frequently prescribed for the prevention or treatment of urinary (49.5%; prevalence: 3.23%) and respiratory (31.8%; prevalence: 1.81%) tract infections. A very high proportion of uroprophylaxis was reported (25.6% of all prescribed antimicrobials; prevalence: 1.67%).ConclusionsThe indications for antimicrobial prescribing varied markedly between countries. We identified uroprophylaxis as a possible target for quality improvement. Copyright © 2012 John Wiley & Sons, Ltd.