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Disentangling the roles of nitrogen dopants and vacancy defects (VG) in metal-free carbon catalysts for the oxygen reduction reaction (ORR) ideally requires studying both the dopants and defects separately. Here, we systematically introduced nitrogen dopants and VGs via plasma treatment into the basal plane of monolayer graphene as a model carbon catalyst to investigate their specific roles in ORR catalysis. An increased defect density including dopants is positively associated with boosted ORR activity. Nitrogen dopants are responsible for an improved current via a 2e- pathway generating hydroperoxide, while VGs result in enhanced kinetics and water production. We therefore infer that VGs in graphene are responsible for the improved ORR kinetics, while nitrogen dopants majorly influence the selectivity of ORR reaction products. The nitrogen dopants without VGs lead to a higher overpotential compared with the pristine graphene. Instead of the attribution of the ORR active site to only nitrogen species in carbon materials, the improved ORR activity in nitrogen-doped carbon materials should be attributed to the active sites constituted of VGs, oxygen dopants, and nitrogen dopants. Through this work, we provide important insights into the intertwined roles of nitrogen and VGs as well as oxygen dopants in nitrogen-doped metal-free catalysts for a more efficient ORR.
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BACKGROUND: Tinnitus is a common problem in patients with a cochlear implant (CI). Between 4% and 25% of CI recipients experience a moderate to severe tinnitus handicap. However, apart from handicap scores, little is known about the real-life impact tinnitus has on those with CIs. We aimed to explore the impact of tinnitus on adult CI recipients, situations impacting tinnitus, tinnitus-related difficulties and their management strategies, using an exploratory sequential mixed-method approach. METHODS: A 2-week web-based forum was conducted using Cochlear Ltd.'s online platform, Cochlear Conversation. A thematic analysis was conducted on the data from the forum discussion to develop key themes and sub-themes. To quantify themes and sub-themes identified, a survey was developed in English with face validity using cognitive interviews, then translated into French, German and Dutch and disseminated on the Cochlear Conversation platform, in six countries (Australia, France, Germany, New Zealand, the Netherlands and United Kingdom). Participants were adult CI recipients experiencing tinnitus who received a Cochlear Ltd. CI after 18 years of age. RESULTS: Four key themes were identified using thematic analysis of the discussion forum: tinnitus experience, situations impacting tinnitus, difficulties associated with tinnitus and tinnitus management. Among the 414 participants of the survey, tinnitus burden on average was a moderate problem without their sound processor and not a problem with the sound processor on. Fatigue, stress, concentration, group conversation and hearing difficulties were the most frequently reported difficulties and was reported to intensify when not wearing the sound processor. For most CI recipients, tinnitus seemed to increase when performing a hearing test, during a CI programming session, or when tired, stressed, or sick. To manage their tinnitus, participants reported turning on their sound processor and avoiding noisy environments. CONCLUSION: The qualitative analysis showed that tinnitus can affect everyday life of CI recipients in various ways and highlighted the heterogeneity in their tinnitus experiences. The survey findings extended this to show that tinnitus impact, related difficulties, and management strategies often depend on sound processor use. This exploratory sequential mixed-method study provided a better understanding of the potential benefits of sound processor use, and thus of intracochlear electrical stimulation, on the impact of tinnitus.
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Implantación Coclear , Implantes Cocleares , Pérdida Auditiva , Percepción del Habla , Acúfeno , Adulto , Humanos , Percepción del Habla/fisiología , Implantación Coclear/métodos , Pérdida Auditiva/complicaciones , Pérdida Auditiva/cirugíaRESUMEN
BackgroundDuring the COVID-19 pandemic, international shipping activity was disrupted as movement of people and goods was restricted. The Port of Rotterdam, the largest port in Europe, remained operational throughout.AimWe describe the burden of COVID-19 among crew on sea-going vessels at the port and recommend improvements in future infectious disease event notification and response at commercial ports.MethodsSuspected COVID-19 cases on sea-going vessels were notified to port authorities and public health (PH) authorities pre-arrival via the Maritime Declaration of Health. We linked data from port and PH information systems between 1 January 2020 and 31 July 2021, derived a notification rate (NR) of COVID-19 events per arrival, and an attack rate (AR) per vessel (confirmed cases). We compared AR by vessel type (workship/tanker/cargo/passenger), during wildtype-, alpha- and delta-dominant calendar periods.ResultsEighty-four COVID-19 events were notified on ships, involving 622 cases. The NR among 45,030 new arrivals was 173 per 100,000 impacting 1% of vessels. Events per week peaked in April 2021 and again in July 2021, when the AR was also highest. Half of all cases were notified on workships, events occurring earlier and more frequently than on other vessels.ConclusionNotification of COVID-19 events on ships occurred infrequently, although case under-ascertainment was likely. Pre-agreed protocols for data-sharing between stakeholders locally and across Europe would facilitate more efficient pandemic response. Public health access to specimens for sequencing and environmental sampling would give greater insight into viral spread on ships.
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COVID-19 , Navíos , Humanos , Países Bajos/epidemiología , Pandemias , COVID-19/epidemiología , Brotes de Enfermedades , Notificación de EnfermedadesRESUMEN
Per- and polyfluoroalkyl substances (PFASs) are omnipresent and have been shown to induce a wide range of adverse health effects, including hepatotoxicity, developmental toxicity, and immunotoxicity. The aim of the present work was to assess whether human HepaRG liver cells can be used to obtain insight into differences in hepatotoxic potencies of a series of PFASs. Therefore, the effects of 18 PFASs on cellular triglyceride accumulation (AdipoRed assay) and gene expression (DNA microarray for PFOS and RT-qPCR for all 18 PFASs) were studied in HepaRG cells. BMDExpress analysis of the PFOS microarray data indicated that various cellular processes were affected at the gene expression level. From these data, ten genes were selected to assess the concentration-effect relationship of all 18 PFASs using RT-qPCR analysis. The AdipoRed data and the RT-qPCR data were used for the derivation of in vitro relative potencies using PROAST analysis. In vitro relative potency factors (RPFs) could be obtained for 8 PFASs (including index chemical PFOA) based on the AdipoRed data, whereas for the selected genes, in vitro RPFs could be obtained for 11-18 PFASs (including index chemical PFOA). For the readout OAT5 expression, in vitro RPFs were obtained for all PFASs. In vitro RPFs were found to correlate in general well with each other (Spearman correlation) except for the PPAR target genes ANGPTL4 and PDK4. Comparison of in vitro RPFs with RPFs obtained from in vivo studies in rats indicate that best correlations (Spearman correlation) were obtained for in vitro RPFs based on OAT5 and CXCL10 expression changes and external in vivo RPFs. HFPO-TA was found to be the most potent PFAS tested, being around tenfold more potent than PFOA. Altogether, it may be concluded that the HepaRG model may provide relevant data to provide insight into which PFASs are relevant regarding their hepatotoxic effects and that it can be applied as a screening tool to prioritize other PFASs for further hazard and risk assessment.
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Ácidos Alcanesulfónicos , Efectos Colaterales y Reacciones Adversas Relacionados con Medicamentos , Fluorocarburos , Humanos , Animales , Ratas , Fluorocarburos/toxicidad , Ácidos Alcanesulfónicos/toxicidad , Hepatocitos , Hígado , Expresión GénicaRESUMEN
H2O2 is a bulk chemical used as "green" alternative in a variety of applications, but has an energy and waste intensive production method. The electrochemical O2 reduction to H2O2 is viable alternative with examples of the direct production of up to 20% H2O2 solutions. In that respect, we found that the dinuclear complex Cu2(btmpa) (6,6'-bis[[bis(2-pyridylmethyl)amino]methyl]-2,2'-bipyridine) reduces O2 to H2O2 with a selectivity up to 90 % according to single linear sweep rotating ring disk electrode measurements. Microbalance experiments showed that complex reduction leads to surface adsorption thereby increasing the catalytic current. More importantly, we kept a high Faradaic efficiency for H2O2 between 60 and 70 % over the course of 2â h of amperometry by introducing high potential intervals to strip deposited copper (depCu). This is the first example of extensive studies into the long term electrochemical O2 to H2O2 reduction by a molecular complex which allowed to retain the high intrinsic selectivity of Cu2(btmpa) towards H2O2 production leading to relevant levels of H2O2.
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Tinnitus is a common symptom in cochlear implant (CI) recipients. There is no clear evidence of the influence of tinnitus on hearing-related quality of life (QoL) in this population. The aim of this study was to assess the relationship between hearing-related QoL measured by the Speech, Spatial and Qualities of Hearing scale (SSQ12) and tinnitus annoyance or perceived change in tinnitus annoyance after cochlear implantation. The study sample consisted of 2322 implanted adults across France, Germany, Ireland, Italy, the Netherlands, Sweden and the United Kingdom. Information relating to QoL measured using the SSQ12 and tinnitus annoyance and change in tinnitus annoyance, assessed using single-item questions, were collected one or more years post-implantation. The relationship between SSQ12 score and tinnitus annoyance or change in tinnitus annoyance was analysed using linear models adjusted for age and unilateral versus bilateral implants. Tukey pairwise tests were used to compare mean SSQ12 scores across levels of tinnitus annoyance and changes. Tinnitus prevalence was 33.9% post-implantation. Recipients with tinnitus had a significantly lower SSQ12 score than recipients without tinnitus. SSQ scores varied significantly with tinnitus annoyance, age and unilateral versus bilateral implants. Overall, CI recipients who experienced less bothersome tinnitus reported better hearing-related QoL. Healthcare professionals should be aware of the influence of tinnitus on CI recipients' hearing to manage patient expectations.
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Implantación Coclear , Implantes Cocleares , Percepción del Habla , Acúfeno , Adulto , Audición , Humanos , Calidad de Vida , Encuestas y Cuestionarios , Acúfeno/etiología , Acúfeno/cirugía , Resultado del TratamientoRESUMEN
The presence of defects and chemical dopants in metal-free carbon materials plays an important role in the electrocatalysis of the oxygen reduction reaction (ORR). The precise control and design of defects and dopants in carbon electrodes will allow the fundamental understanding of activity-structure correlations for tailoring catalytic performance of carbon-based, most particularly graphene-based, electrode materials. Herein, we adopted monolayer graphene - a model carbon-based electrode - for systematical introduction of nitrogen and oxygen dopants, together with vacancy defects, and studied their roles in catalyzing ORR. Compared to pristine graphene, nitrogen doping exhibited a limited effect on ORR activity. In contrast, nitrogen doping in graphene predoped with vacancy defects or oxygen enhanced the activities at 0.4 V vs the reversible hydrogen electrode (RHE) by 1.2 and 2.0 times, respectively. The optimal activity was achieved for nitrogen doping in graphene functionalized with oxygenated defects, 12.8 times more than nitrogen-doped and 7.7 times more than pristine graphene. More importantly, oxygenated defects are highly related to the 4e- pathway instead of nitrogen dopants. This work indicates a non-negligible contribution of oxygen and especially oxygenated vacancy defects for the catalytic activity of nitrogen-doped graphene.
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OBJECTIVES: In pure-tone audiometry, hearing thresholds are typically measured up to 8 kHz. Recent research has shown that extended high-frequency (EHF; frequencies >8 kHz) speech information improves speech recognition. However, it is unclear whether the EHF benefit is present for different types of speech material. This study assesses the added value of EHF information for speech recognition in noise for digit triplets, consonant-vowel-consonant (CVC) words, and sentences; and for speech recognition in quiet for CVC. DESIGN: Twenty-four young adults with normal-hearing thresholds up to 16 kHz performed a listening experiment in quiet and in noise in a within-subject repeated measures design. Stimuli were presented monaurally. Steady state speech-shaped noise at a fixed signal to noise ratio was used for measurements in noise. Listening conditions varied only in terms of available EHF information. Stimuli were presented in three different conditions: (1) both speech and noise broadband, (2) speech broadband and noise low-pass filtered at 8 kHz, and (3) both speech and noise low-pass filtered at 8 kHz. In the speech-in-quiet experiment, stimuli (CVC) were high-pass filtered at 3 kHz and presented in two conditions: (1) with EHF information and (2) without EHF information. RESULTS: In the speech-in-noise experiment, for all speech material, the highest scores were achieved in the condition where the noise was low-pass filtered at 8 kHz and speech unfiltered; the lowest scores were obtained in the condition where both speech and noise were low-pass filtered at 8 kHz. Adding speech frequencies above 8 kHz improved the median recognition scores by 75.0%, 21.8%, and 23.8% for digit triplets, words, and sentences, respectively, at a fixed signal to noise ratio. In the speech-in-quiet experiment, median recognition scores were 7.8% higher in the condition where the EHF information was available, as opposed to when it was not. CONCLUSIONS: Speech information for frequencies above 8 kHz contributes to speech recognition in noise. It also contributes to speech recognition in quiet when information below 3 kHz is absent. Our results suggest that EHFs may be relevant in challenging listening conditions and should be measured in pure-tone audiometry to get a complete picture of a person's hearing. Further, results of speech recognition tests may vary when different recording and/or measurement equipment is used with different frequency responses above 8 kHz.
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Percepción del Habla , Habla , Audiometría de Tonos Puros , Humanos , Ruido , Percepción del Habla/fisiología , Prueba del Umbral de Recepción del Habla , Adulto JovenRESUMEN
Several electrical stimulation patterns of the auditory nerve have been described for tinnitus relief, but there is no consensus on the most effective stimulation pattern. Therefore, we aim to systematically review the literature on the effect of intra- and extracochlear electrical stimulation patterns as a treatment option for patients with tinnitus. Only studies on intra- and extracochlear electrical stimulation for patients with tinnitus were included if the stimulation used did not concern standardized CI stimulation patterns to primarily rehabilitate hearing loss as intervention. A total of 34 studies met the inclusion criteria, with 10 studies (89 patients) on intracochlear electrical stimulation and 25 studies on extracochlear electrical stimulation (1109 patients). There was a high to medium risk of bias in 22 studies, especially due to lack of a non-exposed group and poor selection of the exposed group. All included studies showed subjective tinnitus improvement during or after electrical stimulation, using different stimulation patterns. Due to methodological limitations and low reporting quality of the included studies, the potential of intra- and extracochlear stimulation has not been fully explored. To draw conclusions on which stimulation patterns should be optimized for tinnitus relief, a deeper understanding of the mechanisms involved in tinnitus suppression is needed.
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BACKGROUND: People on ships are at high risk for outbreaks of infectious diseases including coronavirus disease 2019 (COVID-19). A rapid and well-coordinated response is important to curb transmission of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). We studied an outbreak on an industrial ship to improve outbreak control for ships and coordination between participating harbour partners. MATERIALS AND METHODS: Public Health Service (PHS) Rotterdam-Rijnmond performed an epidemiological investigation during the outbreak of COVID-19 among 77 seafarers on a ship in their port. The captain was interviewed about ship details and his experiences during the outbreak. The seafarers were asked to fill in questionnaires about symptoms suspicious of COVID-19 and date of symptom onset. Information about stakeholders involved in outbreak control was registered. RESULTS: The captain first contacted PHS about probable cases on March 31st 2020 via a physician ashore. One crewmember was hospitalised on April 8th and another died unexpectedly aboard on April 10th. Questionnaires distributed mid-April to the 75 remaining seafarers showed that 38 of 60 responders (63%) had had suspicious symptoms between February 15th and April 13th. None of them were tested but a total of 8 other crewmembers tested positive for COVID-19 after leaving the ship, including the hospitalised crewmember and the one who died aboard. On May 5th, the last case left isolation and the quarantine ended. Many different stakeholders were involved in the outbreak response and responsibilities were not always fully clear beforehand, causing coordination issues. CONCLUSIONS: Testing crew with COVID-19 symptoms underpins control measures and clarifies communication between stakeholders. Building a network beforehand to develop outbreak guidelines tailored to ships and local circumstances is essential to control future outbreaks on ships.
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Prueba de COVID-19/estadística & datos numéricos , COVID-19/diagnóstico , Brotes de Enfermedades/prevención & control , Cuarentena , Navíos , Adulto , Humanos , Medicina Naval/métodos , Países Bajos , Estudios Retrospectivos , ViajeRESUMEN
INTRODUCTION: Tinnitus is the perception of sound without an external stimulus, often experienced as a ringing or buzzing sound. Subjective tinnitus is assumed to origin from changes in neural activity caused by reduced or lack of auditory input, for instance due to hearing loss. Since auditory deprivation is thought to be one of the causes of tinnitus, increasing the auditory input by cochlear implantation might be a possible treatment. In studies assessing cochlear implantation for patients with hearing loss, tinnitus relief was seen as a secondary outcome. Therefore, we will assess the effect of cochlear implantation in patients with primarily tinnitus complaints. METHOD AND ANALYSIS: In this randomised controlled trial starting in January 2021 at the ENT department of the UMC Utrecht (the Netherlands), patients with a primary complaint of tinnitus will be included. Fifty patients (Tinnitus Functional Index (TFI) >32, Beck's Depression Index <19, pure tone average at 0.5, 1, 2 and 4 kHz: bilateral threshold between 50 and ≤75 dB) will be randomised towards cochlear implantation or no intervention. Primary outcome of the study is tinnitus burden as measured by the TFI. Outcomes of interest are tinnitus severity, hearing performances (tinnitus pitch and loudness, speech perception), quality of life, depression and patient-related changes. Outcomes will be evaluated prior to implantation and at 3 and 6 months after the surgery. The control group will receive questionnaires at 3 and 6 months after randomisation. We expect a significant difference between the cochlear implant recipients and the control group for tinnitus burden. ETHICS AND DISSEMINATION: This research protocol was approved by the Institutional Review Board of the University Medical Center (UMC) Utrecht (NL70319.041.19, V5.0, January 2021). The trial results will be made accessible to the public in a peer-review journal. TRIAL REGISTRATION NUMBER: Trial registration number NL8693; Pre-results.
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Implantación Coclear , Acúfeno , Adulto , Pérdida Auditiva Bilateral , Humanos , Países Bajos , Calidad de Vida , Ensayos Clínicos Controlados Aleatorios como Asunto , Acúfeno/cirugía , Resultado del TratamientoRESUMEN
To date, the copper complex with the tris(2-pyridylmethyl)amine (tmpa) ligand (Cu-tmpa) catalyzes the ORR with the highest reported turnover frequency (TOF) for any molecular copper catalyst. To gain insight into the importance of the tetradentate nature and high flexibility of the tmpa ligand for efficient four-electron ORR catalysis, the redox and electrocatalytic ORR behavior of the copper complexes of 2,2':6',2â³-terpyridine (terpy) and bis(2-pyridylmethyl)amine (bmpa) (Cu-terpy and Cu-bmpa, respectively) were investigated in the present study. With a combination of cyclic voltammetry and rotating ring disk electrode measurements, we demonstrate that the presence of the terpy and bmpa ligands results in a decrease in catalytic ORR activity and an increase in Faradaic efficiency for H2O2 production. The lower catalytic activity is shown to be the result of a stabilization of the CuI state of the complex compared to the earlier reported Cu-tmpa catalyst. This stabilization is most likely caused by the lower electron donating character of the tridentate terpy and bmpa ligands compared to the tetradentate tmpa ligand. The Laviron plots of the redox behavior of Cu-terpy and Cu-bmpa indicated that the formation of the ORR active catalyst involves relatively slow electron transfer kinetics which is caused by the inability of Cu-terpy and Cu-bmpa to form the preferred tetrahedral coordination geometry for a CuI complex easily. Our study illustrates that both the tetradentate nature of the tmpa ligand and the ability of Cu-tmpa to form the preferred tetrahedral coordination geometry for a CuI complex are of utmost importance for ORR catalysis with very high catalytic rates.
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Cochlear implant users' limited ability to understand speech in noisy environments has been linked to the poor spatial resolution and the high degree of spectral smearing associated with the spread of neural excitation. A sound coding algorithm that aims to improve the spectro-temporal representation of the sound signal at the implanted ear by precompensating the electrical stimulation for the spread of excitation is presented in this study. The spread precompensation algorithm was integrated into the standard clinical advanced combination encoder (ACE) strategy and the resulting strategy was called SPACE. SPACE was evaluated acutely with a group of six implant users and was compared to their daily used ACE strategy in terms of preference rating and speech recognition in four-talker babble and stationary speech-shaped noise. While no significant differences in preference rating were observed, speech recognition in four-talker babble was improved by SPACE processing. Analysis of the group results revealed a significant improvement in mean speech reception threshold (SRT) over the ACE strategy of 1.4 dB in four-talker babble, whereas the difference of 0.9 dB in stationary noise did not reach statistical significance. Assessment of individual differences showed that four out of six listeners obtained significant SRT improvements with SPACE and that no subject scored significantly worse compared to ACE. The results suggest that the proposed sound coding strategy has the potential to improve speech perception for cochlear implant users in challenging listening situations.
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Implantación Coclear , Implantes Cocleares , Audición , Ruido/efectos adversos , Percepción del HablaRESUMEN
Electrochemical water oxidation is the bottleneck of electrolyzers as even the best catalysts, iridium and ruthenium oxides, have to operate at significant overpotentials. Previously, the position of a hydroxyl on a series of hydroxylpicolinate ligands was found to significantly influence the activity of molecular iridium catalysts in sacrificial oxidant driven water oxidation. In this study, these catalysts were tested under electrochemical conditions and benchmarked to several other known molecular iridium catalysts under the exact same conditions. This allowed us to compare these catalysts directly and observe whether structure-activity relationships would prevail under electrochemical conditions. Using both electrochemical quartz crystal microbalance experiments and X-ray photoelectron spectroscopy, we found that all studied iridium complexes form an iridium deposit on the electrode with binding energies ranging from 62.4 to 62.7 eV for the major Ir 4f7/2 species. These do not match the binding energies found for the parent complexes, which have a broader binding energy range from 61.7 to 62.7 eV and show a clear relationship to the electronegativity induced by the ligands. Moreover, all catalysts performed the electrochemical water oxidation in the same order of magnitude as the maximum currents ranged from 0.2 to 0.6 mA cm-2 once more without clear structure-activity relationships. In addition, by employing 1H NMR spectroscopy we found evidence for Cp* breakdown products such as acetate. Electrodeposited iridium oxide from ligand free [Ir(OH)6]2- or a colloidal iridium oxide nanoparticles solution produces currents almost 2 orders of magnitude higher with a maximum current of 11 mA cm-2. Also, this deposited material contains, apart from an Ir 4f7/2 species at 62.4 eV, an Ir species at 63.6 eV, which is not observed for any deposit formed by the molecular complexes. Thus, the electrodeposited material of the complexes cannot be directly linked to bulk iridium oxide. Small IrOx clusters containing few Ir atoms with partially incorporated ligand residues are the most likely option for the catalytically active electrodeposit. Our results emphasize that structure-activity relationships obtained with sacrificial oxidants do not necessarily translate to electrochemical conditions. Furthermore, other factors, such as electrodeposition and catalyst degradation, play a major role in the electrochemically driven water oxidation and should thus be considered when optimizing molecular catalysts.
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BACKGROUND: The Asthma Control Test (ACT) has been used to assess asthma control in both clinical trials and clinical practice. However, the relationships between ACT score and other measures of asthma impact are not fully understood. Here, we evaluate how ACT scores relate to other clinical, patient-reported, or economic asthma outcomes. METHODS: A targeted literature search of online databases and conference abstracts was performed. Data were extracted from articles reporting ACT score alongside one or more of: Asthma Control Questionnaire (ACQ) score; rescue medication use; exacerbations; lung function; health-/asthma-related quality of life (QoL); sleep quality; work and productivity; and healthcare resource use (HRU) and costs. RESULTS: A total of 1653 publications were identified, 74 of which were included in the final analysis. Of these, 69 studies found that improvement in ACT score was related to improvement in outcome(s), either as correlation or by association. The level of evidence for each relationship differed widely between outcomes: substantial evidence was identified for relationships between ACT score and ACQ score, lung function, and asthma-related QoL; moderate evidence was obtained for relationships between ACT score and rescue medication use, exacerbations, sleep quality, and work and productivity; limited evidence was identified for relationships between ACT score and general health-related QoL, HRU, and healthcare costs. CONCLUSIONS: Findings of this review suggest that the ACT is an appropriate measure for overall asthma impact and support its use in clinical trial settings. GlaxoSmithKline plc. study number HO-17-18170.
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Asma/diagnóstico , Índice de Severidad de la Enfermedad , Encuestas y Cuestionarios , Asma/terapia , Ensayos Clínicos como Asunto , Progresión de la Enfermedad , Humanos , Calidad de VidaRESUMEN
Dinuclear CuII complexes bearing two 3,5-diamino-1,2,4-triazole (DAT) ligands have gained considerable attention as a potential model system for laccase due to their low overpotential for the oxygen reduction reaction (ORR). In this study, the active species for the ORR was investigated. The water soluble dinuclear copper complex (Cu(DAT)) was obtained by mixing a 1 : 1 ratio of Cu(OTf)2 and DAT in water. The electron paramagnetic resonance (EPR) spectrum of Cu(DAT) showed a broad axial signal with a g factor of 2.16 as well as a low intensity Ms = ±2 absorption characteristic of the Cu2(µ-DAT)2 moiety. Monitoring the typical 380 nm peak with UV-Vis spectroscopy revealed that the Cu2(µ-DAT)2 core is extremely sensitive to changes in pH, copper to ligand ratios and the presence of anions. Electrochemical quartz crystal microbalance experiments displayed a large decrease in frequency below 0.5 V versus the reversible hydrogen electrode (RHE) in a Cu(DAT) solution implying the formation of deposition. Rotating ring disk electrode experiments showed that this deposition is an active ORR catalyst which reduces O2 all the way to water at pH 5. The activity increased significantly in the course of time. X-ray photoelectron spectroscopy was utilized to analyze the composition of the deposition. Significant shifts in the Cu 2p3/2 and N 1s spectra were observed with respect to Cu(DAT). After ORR catalysis at pH 5, mostly CuI and/or Cu0 species are present and the deposition corresponds to previously reported electrodepositions of copper. This leads us to conclude that the active species is of a heterogeneous nature and lacks any structural similarity with laccase.
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BACKGROUND: Although for most cochlear implant (CI) users good speech understanding is reached (at least in quiet environments), the perception and the appraisal of music are generally unsatisfactory. PURPOSE: The improvement in music appraisal was evaluated in CI participants by using a stereo music preprocessing scheme implemented on a take-home device, in a comfortable listening environment. The preprocessing allowed adjusting the balance among vocals/bass/drums and other instruments, and was evaluated for different genres of music. The correlation between the preferred settings and the participants' speech and pitch detection performance was investigated. RESEARCH DESIGN: During the initial visit preceding the take-home test, the participants' speech-in-noise perception and pitch detection performance were measured, and a questionnaire about their music involvement was completed. The take-home device was provided, including the stereo music preprocessing scheme and seven playlists with six songs each. The participants were asked to adjust the balance by means of a turning wheel to make the music sound most enjoyable, and to repeat this three times for all songs. STUDY SAMPLE: Twelve postlingually deafened CI users participated in the study. DATA COLLECTION AND ANALYSIS: The data were collected by means of a take-home device, which preserved all the preferred settings for the different songs. Statistical analysis was done with a Friedman test (with post hoc Wilcoxon signed-rank test) to check the effect of "Genre." The correlations were investigated with Pearson's and Spearman's correlation coefficients. RESULTS: All participants preferred a balance significantly different from the original balance. Differences across participants were observed which could not be explained by perceptual abilities. An effect of "Genre" was found, showing significantly smaller preferred deviation from the original balance for Golden Oldies compared to the other genres. CONCLUSIONS: The stereo music preprocessing scheme showed an improvement in music appraisal with complex music and hence might be a good tool for music listening, training, or rehabilitation for CI users.
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Percepción Auditiva/fisiología , Implantación Coclear/métodos , Implantes Cocleares , Pérdida Auditiva/cirugía , Música , Percepción del Habla/fisiología , Adulto , Factores de Edad , Anciano , Umbral Auditivo/fisiología , Estudios de Cohortes , Femenino , Pérdida Auditiva/diagnóstico , Humanos , Masculino , Persona de Mediana Edad , Medición de Riesgo , Estadísticas no ParamétricasRESUMEN
OBJECTIVE: Cochlear implants (CI) and hearing aids (HA) have a gain control that allows the bimodal user to change the loudness. Due to differences in dynamic range between CI and HA, an equal change of the gains of the two devices results in different changes in loudness. The objective was to relate and individualise the step sizes of the loudness controls to obtain a similar perceptual effect in the two ears. DESIGN: We used loudness models parametrised for individual users to find a relation between the controls of the CI and the HA such that each step resulted in an equal change in loudness. We conducted loudness balancing experiments to validate the results. STUDY SAMPLE: Eleven bimodal users of whom six were tested in a prior study. RESULTS: The difference between the optimal gain from the loudness balancing procedure and actual gain was 3.3 dB when the new relation was applied. In contrast, the difference was 8 dB if equal step sized were applied at both sides. CONCLUSION: We can relate the controls such that each step results in a similar loudness difference.
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Implantación Coclear/instrumentación , Implantes Cocleares , Corrección de Deficiencia Auditiva/instrumentación , Sordera/rehabilitación , Audífonos , Percepción Sonora , Personas con Deficiencia Auditiva/rehabilitación , Percepción del Habla , Estimulación Acústica , Adolescente , Adulto , Anciano , Sordera/diagnóstico , Sordera/fisiopatología , Sordera/psicología , Estimulación Eléctrica , Audición , Humanos , Persona de Mediana Edad , Personas con Deficiencia Auditiva/psicología , Diseño de Prótesis , Procesamiento de Señales Asistido por Computador , Inteligibilidad del HablaRESUMEN
Speech understanding in noisy environments is still one of the major challenges for cochlear implant (CI) users in everyday life. We evaluated a speech enhancement algorithm based on neural networks (NNSE) for improving speech intelligibility in noise for CI users. The algorithm decomposes the noisy speech signal into time-frequency units, extracts a set of auditory-inspired features and feeds them to the neural network to produce an estimation of which frequency channels contain more perceptually important information (higher signal-to-noise ratio, SNR). This estimate is used to attenuate noise-dominated and retain speech-dominated CI channels for electrical stimulation, as in traditional n-of-m CI coding strategies. The proposed algorithm was evaluated by measuring the speech-in-noise performance of 14 CI users using three types of background noise. Two NNSE algorithms were compared: a speaker-dependent algorithm, that was trained on the target speaker used for testing, and a speaker-independent algorithm, that was trained on different speakers. Significant improvements in the intelligibility of speech in stationary and fluctuating noises were found relative to the unprocessed condition for the speaker-dependent algorithm in all noise types and for the speaker-independent algorithm in 2 out of 3 noise types. The NNSE algorithms used noise-specific neural networks that generalized to novel segments of the same noise type and worked over a range of SNRs. The proposed algorithm has the potential to improve the intelligibility of speech in noise for CI users while meeting the requirements of low computational complexity and processing delay for application in CI devices.