Homogeneous Catalytic CO2 Hydrogenation by [Fe]-Hydrogenase Bioinspired Complexes: A Computational Study.

Computational modeling at the DLPNO-CCSD(T)/CBS//M06-L/def2-TZVP level of theory was used to propose four different iron catalysts whose structures were inspired on the [Fe]-hydrogenase active site: [Fe(MePNNHNP)(acmp)] (C(1), MePNNHNP = 2,6-bis(dimethylphosphine), acmp = acylmethylpyridine), [Fe(CNNHNC)(acmp)] (C(2), CNNHNC = 2,6-bis(methylimidazol-2-ylidene)), [Fe(MePNNNP)(acmp)] (D(1), MePNNNP = 2,6-bis((dimethylphosphine)pyridine)), and [Fe(CNNNC)(acmp)] (D(2), CNNNC = 2,6-bis((methylimidazol-2-ylidene) pyridine)). Through these electronic structure calculations, the catalytic mechanism of the reaction was explored. The intermediates and transition states present along the reaction coordinate were identified and described as to their equilibrium geometries, vibrational frequencies, and energies. Quasi-harmonic corrections were performed considering conditions analogous to those used experimentally. To compare the catalytic activities of the studied catalysts, turnover frequencies (TOFs) were calculated. Based on the explored catalytic cycles and TOF values (D(1) > C(1) > D(2) > C(2)), the most suitable iron catalysts are those with tridentate phosphine pincer-type ligands coordinated to the metal center. These systems are new promising iron catalysts to promote the CO2 hydrogenation to formic acid without any use of bases or additives.

DFT study of H2 adsorption at a Cu-SSZ-13 zeolite: a cluster approach.

In this work the H2 adsorption at a Cu(i)-SSZ-13 exchanged zeolite was theoretically investigated. A systematic cluster approach was used and different density functionals (B3LYP, B3LYP-D3(BJ), M06L, PBE, PBE-D3(BJ) and ωB97XD) and a def2-SVP basis set were benchmarked. In order to select the best approach to the H2 adsorption over a Cu(i)-SSZ-13 cluster with 78 atoms (16 T-sites), two main tasks were performed: (1) a comparison between theoretical and experimental structures and (2) a comparison between theoretical and experimental adsorption enthalpies. By employing the most suitable functional - the ωB97X-D - the H2 interaction with the zeolite structure was studied by means of NBO, NCI, AIM and DLPNO-CCSD(T)/LED analyses.

Theoretical study on selectivity trends in (N-heterocyclic carbene)-Pd catalyzed mizoroki-heck reactions: Exploring density functionals methods and molecular models.

The regioselectivity of the NHC-Pd catalyzed Heck coupling reaction between phenyl bromide and styrene has been investigated using the density functional theory, wave-function (WF)-based methods and two different sizes of model ligands. In addition to the WF methods, the TPSS-D3, ω B97X-D, BP86-D3, and M06-L density functionals were reliable approaches to be applied, independently of the basis set. Moreover, the NCI analysis showed that weak interactions are important forces to be taken into account when exploring the regioselectivity of this reaction, mainly when a crowded NHC ligand is present. © 2017 Wiley Periodicals, Inc.

Pediatric Voice Handicap Index (pVHI): Validation in European Portuguese Children.

OBJECTIVES: To determine reliability and validity of the European Portuguese pVHI version (pVHI-EP). STUDY DESIGN: Cross-sectional design. METHODS: The pVHI-EP and the talkative and global voice assessment scales were administered to the caregivers of children aged from 3 to 16 years old with and without dysphonia. Reliability (internal consistency and test-retest) was analyzed. The validity analyses performed were: (1) content validity by analyzing the percentage of missing data; (2) construct validity with intraclass correlation coefficients among pVHI-EP domains and overall score; (3) concurrent validity was conducted between pVHI-EP, the caregivers' judgment of the child's voice severity on a visual analog scale and the Speech-Language Pathologist perceptual voice assessment; (4) known-groups validity between children with and without dysphonia, and (5) predictive validity by calculating receiver operating characteristics, sensitivity and specificity and determining cut-off points. RESULTS: A total of 283 children (61.5% boys, mean age 8.3 years) participated in the study. The pVHI-EP showed an excellent internal consistency for the pVHI-EP total data. Strong to moderate test-retest reliability confirms pVHI-EP reproducibility. Excellent to good intraclass correlation coefficients between the pVHI-EP overall and the domains confirms its construct validity. Weak to moderate concurrent validity with visual analog scale and Speech-Language Pathologist perceptual voice assessment was confirmed. The pVHI-EP significantly distinguished two groups of different voice conditions. A cut-off point of 10.5 with 95.9% sensitivity and 92.5% specificity was determined for the overall score of the pVHI-EP. CONCLUSIONS: The pVHI-EP is a reliable and valid caregiver voice outcome tool for EP children with dysphonia.

A theoretical study of SnF2+, SnCl2+, and SnO2+ and their experimental search.

We present a detailed theoretical study of the stability of the gas-phase diatomic dications SnF(2+), SnCl(2+), and SnO(2+) using ab initio computer calculations. The ground states of SnF(2+), SnCl(2+), and SnO(2+) are thermodynamically stable, respectively, with dissociation energies of 0.45, 0.30, and 0.42 eV. Whereas SnF(2+) dissociates into Sn(2+) + F, the long range behaviour of the potential energy curves of SnCl(2+) and SnO(2+) is repulsive and wide barrier heights due to avoided crossing act as a kind of effective dissociation energy. Their equilibrium internuclear distances are 4.855, 5.201, and 4.852 a(0), respectively. The double ionisation energies (T(e)) to form SnF(2+), SnCl(2+), and SnO(2+) from their respective neutral parents are 25.87, 23.71, and 25.97 eV. We combine our theoretical work with the experimental results of a search for these doubly positively charged diatomic molecules in the gas phase. SnO(2+) and SnF(2+) have been observed for prolonged oxygen ((16)O(-)) ion beam sputtering of a tin metal foil and of tin (II) fluoride (SnF(2)) powder, respectively, for ion flight times of about 10(-5) s through a magnetic-sector mass spectrometer. In addition, SnCl(2+) has been detected for (16)O(-) ion surface bombardment of stannous (tin (II)) chloride (SnCl(2)) powder. To our knowledge, SnF(2+) is a novel gas-phase molecule, whereas SnCl(2+) had been detected previously by electron-impact ionization mass spectrometry, and SnO(2+) had been observed before by spark source mass spectrometry as well as by atom probe mass spectrometry. We are not aware of any previous theoretical studies of these molecular systems.

Excited electronic states, transition probabilities, and radiative lifetimes of CAs: a theoretical contribution and challenge to experimentalists.

High-level CASSCF/MRCI calculations with a quintuple-ζ quality basis set are reported by characterizing for the first time a manifold of electronic states of the CAs radical yet to be investigated experimentally. Along with the potential energy curves and the associated spectroscopic constants, the dipole moment functions for selected electronic states as well as the transition dipole moment functions for the most relevant electronic transitions are also presented. Estimates of radiative transition probabilities and lifetimes complement this investigation, which also assesses the effect of spin-orbit interaction on the A (2)Π state. Whenever pertinent, comparisons of similarities and differences with the isovalent CN and CP radicals are made.

Incorporation of Chlorella vulgaris and Spirulina maxima biomass in pasta products. Part 1: Preparation and evaluation.

BACKGROUND: Microalgae are able to enhance the nutritional content of conventional foods and hence to positively affect human health, due to their original chemical composition. The aim of the present study was to prepare fresh spaghetti enriched with different amounts of microalgae biomass (Chlorella vulgaris and Spirulina maxima) and to compare the quality parameters (optimal cooking time, cooking losses, swelling index and water absorption), chemical composition, instrumental texture and colour of the raw and cooked pasta enriched with microalgae biomass with standard semolina spaghetti. RESULTS: The incorporation of microalgae results in an increase of quality parameters when compared to the control sample. The colour of microalgae pastas remained relatively stable after cooking. The addition of microalgae resulted in an increase in the raw pasta firmness when compared to the control sample. Of all the microalgae studied, an increase in the biomass concentration (0.5-2.0%) resulted in a general tendency of an increase in the pasta firmness. Sensory analysis revealed that microalgae pastas had higher acceptance scores by the panellists than the control pasta. CONCLUSION: Microalgae pastas presented very appellative colours, such as orange and green, similar to pastas produced with vegetables, with nutritional advantages, showing energetic values similar to commercial pastas. The use of microalgae biomass can enhance the nutritional and sensorial quality of pasta, without affecting its cooking and textural properties.

Double-Blind, Randomized, Placebo-Controlled Phase III Clinical Trial to Evaluate the Efficacy and Safety of treating Healthcare Professionals with the Adsorbed COVID-19 (Inactivated) Vaccine Manufactured by Sinovac - PROFISCOV: A structured summary of a study protocol for a randomised controlled trial.

OBJECTIVES: To evaluate the efficacy of two doses of the adsorbed vaccine COVID-19 (inactivated) produced by Sinovac in symptomatic individuals, with virological confirmation of COVID-19, two weeks after the completion of the two-dose vaccination regimen, aged 18 years or older who work as health professionals providing care to patients with possible or confirmed COVID-19. To describe the occurrence of adverse reactions associated with the administration of each of two doses of the adsorbed vaccine COVID-19 (inactivated) produced by Sinovac up to one week after vaccination in Adults (18-59 years of age) and Elderly (60 years of age or more). TRIAL DESIGN: This is a Phase III, randomized, multicenter, endpoint driven, double-blind, placebo-controlled clinical trial to assess the efficacy and safety of the adsorbed vaccine COVID-19 (inactivated) produced by Sinovac. The adsorbed vaccine COVID-19 (inactivated) produced by Sinovac (product under investigation) will be compared to placebo. Voluntary participants will be randomized to receive two intramuscular doses of the investigational product or the placebo, in a 1: 1 ratio, stratified by age group (18 to 59 years and 60 years or more) and will be monitored for one year by active surveillance of COVID-19. Two databases will be established according to the age groups: one for adults (18-59 years) and one for the elderly (60 years of age or older). The threshold to consider the vaccine efficacious will be to reach a protection level of at least 50%, as proposed by the World Health Organization and the FDA. Success in this criterion will be defined by sequential monitoring with adjustment of the lower limit of the 95% confidence interval above 30% for the primary efficacy endpoint. PARTICIPANTS: Healthy participants and / or participants with clinically controlled disease, of both genders, 18 years of age or older, working as health professionals performing care in units specialized in direct contact with people with possible or confirmed cases of COVID-19. Participation of pregnant women and those who are breastfeeding, as well as those intending to become pregnant within three months after vaccination will not be allowed. Participants will only be included after signing the voluntary Informed Consent Form and ensuring they undergo screening evaluation and conform to all the inclusion and exclusion criteria. All the clinical sites are located in Brazil. INTERVENTION AND COMPARATOR: Experimental intervention: The vaccine was manufactured by Sinovac Life Sciences (Beijing, China) and contains 3 µg/0.5 mL (equivalent to 600 SU per dose) of inactivated SARS-CoV-2 virus, and aluminium hydroxide as adjuvant. Control comparator: The placebo contains aluminium hydroxide in a 0.5 mL solution The schedule of both, experimental intervention and placebo is two 0.5 mL doses IM (deltoid) with a two week interval. MAIN OUTCOMES: The primary efficacy endpoint is the incidence of symptomatic cases of virologically confirmed COVID-19 two weeks after the second vaccination. The virological diagnosis will be confirmed by detection of SARS-CoV-2 nucleic acid in a clinical sample. The primary safety endpoint is the frequency of solicited and unsolicited local and systemic adverse reactions during the period of one week after vaccination according to age group in adult (18-59 years old) and elder (60 years of age or older) subjects. Adverse reactions are defined as adverse events that have a reasonable causal relationship to vaccination. RANDOMISATION: There will be two randomization lists, one for each age group, based on the investigational products to be administered, i.e., vaccine or placebo at a 1: 1 ratio. Each randomization list will be made to include up to 11,800 (18-59 year-old) adults, and 1,260 elderly (60 y-o and older) participants, the maximum number of participants needed per age group. An electronic central randomization system will be used to designate the investigational product that each participant must receive. BLINDING (MASKING): This trial is designed as a double-blind study to avoid introducing bias in the evaluation of efficacy, safety and immunogenicity. The clinical care team, the professionals responsible for the vaccination and the participants will not know which investigational product will be administered. Only pharmacists or nurses in the study who are responsible for the randomization, separation and blinding of the investigational product will have access to unblinded information. The sponsor's operational team will also remain blind. NUMBERS TO BE RANDOMISED (SAMPLE SIZE): The total number of participants needed to evaluate efficacy, 13,060 participants, satisfies the needed sample size calculated to evaluate safety. Therefore, the total number obtained for efficacy will be the number retained for the study. Up to 13,060 participants are expected to enter the study, with up to 11,800 participants aged 18 to 59 years and 1,260 elderly participants aged 60 and over. Half of the participants of each group will receive the experimental vaccine and half of them will receive the placebo. The recruitment of participants may be modified as recommended by the Data Safety Monitoring Committee at time of the interim unblinded analysis or blind assessment of the COVID-19 attack rate during the study. TRIAL STATUS: Protocol version 2.0 - 24-Aug-2020. Recruitment started on July 21st, 2020. The recruitment is expected to conclude in October 2020. TRIAL REGISTRATION: ClinicalTrials.gov Identifier: NCT0445659 . Registry on 2 July 2020 FULL PROTOCOL: The full protocol is attached as an additional file, accessible from the Trials website (Additional file 1). In the interest in expediting dissemination of this material, the familiar formatting has been eliminated; this Letter serves as a summary of the key elements of the full protocol.

Microalgae as Functional Ingredients in Savory Food Products: Application to Wheat Crackers.

Crackers are widely consumed snack foods and there is an increasing trend in adding functional ingredients to their composition. In the present work, the dried biomasses of four microalgae strains-Arthrospira platensis F&M-C256, Chlorella vulgaris Allma, Tetraselmis suecica F&M-M33, and Phaeodactylum tricornutum F&M-M40-were used as a source of proteins, antioxidants, and other bioactive molecules in artisanal wheat crackers. Two incorporation levels were tested: 2% (w/w) and 6% (w/w). The impact of microalgae addition was evaluated in terms of physical properties, biochemical composition, antioxidant activity, in vitro digestibility, and sensory characteristics. Microalgae crackers presented stable color and texture throughout eight weeks of storage. Microalgae crackers were slightly thinner and lighter than the control but presented a similar density in agreement with scanning electron microscope images, indicating that gas retention was not greatly affected by microalgae addition. Regarding biochemical composition, 6% A. platensis and C. vulgaris crackers presented a significantly higher protein content (13.2-13.5%), for which they could be claimed to be a "source of protein" according to the Regulation (EC) No. 1924/2006. A. platensis crackers showed the highest antioxidant activity and attained better sensory analysis scores. T. suecica and P. tricornutum crackers showed high phenolic content and antioxidant activity but attained low sensory scores mainly because of their unattractive fishy off-flavor.

Development of new microalgae-based sourdough "crostini": functional effects of Arthrospira platensis (spirulina) addition.

The aim of this work was to evaluate the influence of Arthrospira platensis F&M-C256 (spirulina) incorporation on the nutritional and functional properties of "crostini", a leavened bakery product largely consumed in Italy and Europe. Sourdough was used as leavening and fermentation agent and three concentrations of A. platensis F&M-C256 were tested: 2%, 6% and 10% (w/w). Despite a lower volume increase compared to the control, the A. platensis F&M-C256 "crostini" doughs reached a technological appropriate volume after fermentation. At the end of fermentation, no significant differences in microorganisms concentrations were observed. A. platensis F&M-C256 "crostini" showed higher protein content compared to the control. Considering the European Commission Regulation on nutritional claims, "crostini" incorporated with 6% and 10% biomass can be claimed to be a "source of protein". Six and ten percent A. platensis "crostini" also presented significantly higher antioxidant capacity and phenolics. A significantly lower value of in vitro dry matter and protein digestibility between A. platensis F&M-C256 "crostini" and the control was found. The overall acceptability decreased with increasing A. platensis F&M-C256 addition. The combination of spirulina biomass addition and the sourdough technology led to the development of a novel microalgae-based bakery product with nutritional and functional features.

How To Arrive at Accurate Benchmark Values for Transition Metal Compounds: Computation or Experiment?

With the objective of analyzing which kind of reference data is appropriate for benchmarking quantum chemical approaches for transition metal compounds, we present the following, (a) a collection of 60 transition metal diatomic molecules for which experimentally derived dissociation energies, equilibrium distances, and harmonic vibrational frequencies are known and (b) a composite computational approach based on coupled-cluster theory with basis set extrapolation, inclusion of core-valence correlation, and corrections for relativistic and multireference effects. The latter correction was obtained from internally contracted multireference coupled-cluster (icMRCC) theory. This composite approach has been used to obtain the dissociation energies and spectroscopic constants for the 60 molecules in our data set. In accordance with previous studies on a subset of molecules, we find that multireference corrections are rather small in many cases and CCSD(T) can provide accurate reference values, if the complete basis set limit is explored. In addition, the multireference correction improves the results in cases where CCSD(T) is not a good approximation. For a few cases, however, strong deviations from experiment persist, which cannot be explained by the remaining error in the computational approach. We suggest that these experimentally derived values require careful revision. This also shows that reliable reference values for benchmarking approximate computational methods are not always easily accessible via experiment and accurate computations may provide an alternative way to access them. In order to assess how the choice of reference data affects benchmark studies, we tested 10 DFT functionals for the molecules in the present data set against experimental and calculated reference values. Despite the differences between these two sets of reference values, we found that the ranking of the relative performance of the DFT functionals is nearly independent of the chosen reference.

Computationally Designed 1,2,4-Triazolylidene-Derived N-Heterocyclic Olefins for CO2 Capture, Activation, and Storage.

In this article, triazolylidene-derived N-heterocyclic olefins (trNHOs) are designed using computational quantum tools, and their potential to promote CO2 sequestration is tested and discussed in detail. The low barrier heights related to the trNHO-mediated process indicate that the tailored compounds are very promising for fast CO2 sequestration. The systematic analysis of the presence of distinct substitutes at different N positions of the trNHO ring allows us to rationalize their effect on the carboxylation process and reveal the best N-substituted trNHO systems for CO2 sequestration and improved trNHO carboxylates for faster CO2 capture/release.

CO2 utilization in the production of biomass and biocompounds by three different microalgae.

The atmospheric CO2 increase is considered the main cause of global warming. Microalgae are photosynthetic microorganisms that can help in CO2 mitigation and at the same time produce value-added compounds. In this study, Scenedesmus obliquus, Chlorella vulgaris, and Chlorella protothecoides were cultivated under 0.035 (air), 5 and 10% (v/v) of CO2 concentrations in air to evaluate the performance of the microalgae in terms of kinetic growth parameters, theoretical CO2 biofixation rate, and biomass composition. Among the microalgae studied, S. obliquus presented the highest values of specific growth rate (µ = 1.28 d-1), maximum productivities (P max = 0.28 g L-1d-1), and theoretical CO2 biofixation rates (0.56 g L-1d-1) at 10% CO2. The highest oil content was found at 5% CO2, and the fatty acid profile was not influenced by the concentration of CO2 in the inflow gas mixture and was in compliance with EN 14214, being suitable for biodiesel purposes. The impact of the CO2 on S. obliquus cells' viability/cell membrane integrity evaluated by the in-line flow cytometry is quite innovative and fast, and revealed that 86.4% of the cells were damaged/permeabilized in cultures without the addition of CO2.

Wastes valorization from Rhodosporidium toruloides NCYC 921 production and biorefinery by anaerobic digestion.

Yeast production and biomass biorefinery processes for lipid and carotenoid extraction generate residues that can be used as substrates for anaerobic digestion. Glucose and carob pulp syrups were used as carbon sources to produce the yeast biomass. The yeast cultivation broth, yeast biomass residues (after carotenoid and lipid extraction) and the carob pulp solid residues obtained from the extraction of sugars were used to produce biogas by applying different Substrate/Inoculum ratios (S/I of 0.5 and 0.75). For all the residues studied, the digestions at the S/I ratio of 0.75 provided higher biogas yields than those carried out at the S/I ratio of 0.5. The best results in terms of biogas production and methane yield were observed for the yeast residue digestion at S/I of 0.75 (65.9mL, 333.7mLg-1VS-1 substrate). As monitored through flow cytometry, its bacterial consortium showed the lowest proportion of injured cells.

Degradation and acute toxicity removal of the antidepressant Fluoxetine (Prozac(®)) in aqueous systems by electron beam irradiation.

Electron beam irradiation (EBI) has been considered an advanced technology for the treatment of water and wastewater, whereas very few previous investigations reported its use for removing pharmaceutical pollutants. In this study, the degradation of fluoxetine (FLX), an antidepressant marketed as Prozac(®), was investigated by using EBI at FLX initial concentration of 19.4 ± 0.2 mg L(-1). More than 90 % FLX degradation was achieved at 0.5 kGy, with FLX below the detection limit (0.012 mg L(-1)) at doses higher than 2.5 kGy. The elucidation of organic byproducts performed using direct injection mass spectrometry, along with the results of ion chromatography, indicated hydroxylation of FLX molecules with release of fluoride and nitrate anions. Nevertheless, about 80 % of the total organic carbon concentration remained even for 7.5 kGy or higher doses. The decreases in acute toxicity achieved 86.8 and 9.6 % for Daphnia similis and Vibrio fischeri after EBI exposure at 5 kGy, respectively. These results suggest that EBI could be an alternative to eliminate FLX and to decrease residual toxicity from wastewater generated in pharmaceutical formulation facilities, although further investigation is needed for correlating the FLX degradation mechanism with the toxicity results.

Correlating the chemical and spectroscopic characteristics of natural organic matter with the photodegradation of sulfamerazine.

The role of aquatic natural organic matter (NOM) in the removal of contaminants of emerging concern has been widely studied. Sulfamerazine (SMR), a sulfonamide antibiotic detected in aquatic environments, is implicated in environmental toxicity and may contribute to the resistance of bacteria to antibiotics. In aquatic systems sulfonamides may undergo direct photodegradation, and, indirect photodegradation through the generation of reactive species. Because some forms of NOM inhibit the photodegradation there is an increasing interest in correlating the spectroscopic parameters of NOM as potential indicators of its degradation in natural waters. Under the conditions used in this study, SMR hydrolysis was shown to be negligible; however, direct photolysis is a significant in most of the solutions studied. Photodegradation was investigated using standard solutions of NOM: Suwannee River natural organic matter (SRNOM), Suwannee River humic acid (SRHA), Suwannee River fulvic acid (SRFA), and Aldrich humic acid (AHA). The steady-state concentrations and formation rates of the reactive species and the SMR degradation rate constants (k1) were correlated with NOM spectroscopic parameters determined using UV-vis absorption, excitation-emission matrix (EEM) fluorescence spectroscopy, and proton nuclear magnetic resonance ((1)H NMR). SMR degradation rate constants (k1) were correlated with steady-state concentrations of NOM triplet-excited state ([(3)NOM(∗)]ss) and the corresponding formation rates ((3)NOM*) for SRNOM, SRHA, and AHA. The efficiency of SMR degradation was highest in AHA solution and was inhibited in solutions of SRFA. The steady-state concentrations of singlet oxygen ([(1)O2]ss) and the SMR degradation rate constants with singlet oxygen (k1O2) were linearly correlated with the total fluorescence and inversely correlated with the carbohydrate/protein content ((1)H NMR) for all forms of NOM. The total fluorescence and EEMs Peak A were confirmed as indicators of (1)O2 formation. Specific ultraviolet absorbance at 254 nm (SUVA254) and aromaticity showed potential correlations with the steady-state concentrations of hydroxyl radical ([HO]ss) and the corresponding formation rates (HO).

Accessing gelling ability of vegetable proteins using rheological and fluorescence techniques.

This work aims to present a comprehensive study about the macroscopic characteristics of globular vegetable proteins, in terms of their gelling ability, by understanding their molecular behaviour, when submitted to a thermal gelling process. The gels of soy, pea and lupin proteins were characterized by rheological techniques. Gelation kinetics, mechanical spectra, as well as the texture of these gels were analyzed and compared. Additionally, capillary viscometry, steady-state fluorescence and fluorescence anisotropy were used to monitor the structural changes induced by the thermal denaturation, which constitutes the main condition for the formation of a gel structure. Based on these techniques it was possible to establish a relationship between the gelling ability of each protein isolate and their structural resistance to thermal unfolding, enabling us to explain the weakest and the strongest gelling ability observed for lupin and soy proteins isolates, respectively.

The Effect of Anchors and Training on the Reliability of Voice Quality Ratings for Different Types of Speech Stimuli.

OBJECTIVE: The main objective of the present study was to investigate if the type of voice stimuli-sustained vowel, oral reading, and connected speech-results in good intrarater and interrater agreement/reliability. STUDY DESIGN: A short-term panel study was performed. METHODS: Voice samples from 30 native European Portuguese speakers were used in the present study. The speech materials used were (1) the sustained vowel /a/, (2) oral reading of the European Portuguese version of "The Story of Arthur the Rat," and (3) connected speech. After an extensive training with textual and auditory anchors, the judges were asked to rate the severity of dysphonic voice stimuli using the phonation dimensions G, R, and B from the GRBAS scale. The voice samples were judged 6 months and 1 year after the training. RESULTS: Intrarater agreement and reliability were generally very good for all the phonation dimensions and voice stimuli. The highest interrater reliability was obtained using the oral reading stimulus, particularly for phonation dimensions grade (G) and breathiness (B). Roughness (R) was the voice quality that was the most difficult to evaluate, leading to interrater unreliability in all voice quality ratings. CONCLUSIONS: Extensive training using textual and auditory anchors and the use of anchors during the voice evaluations appear to be good methods for auditory-perceptual evaluation of dysphonic voices. The best results of interrater reliability were obtained when the oral reading stimulus was used. Breathiness appears to be a voice quality that is easier to evaluate than roughness.

The prevalence of laryngeal pathologies in an academic population.

OBJECTIVE: The main purposes of the present study were to determine the prevalence of laryngeal pathology and voice disorders and to identify their associated risk factors among the workers, teachers, and nonteachers, from a Portuguese university. STUDY DESIGN: Cross-sectional study. METHODOLOGY: A total of 101 participants have volunteered to participate in a voice survey. Data were collected using a questionnaire followed by the diagnosis of laryngeal pathology based on the videolaryngoscopic examination conducted by experienced otolaryngologists. RESULTS: The mean age of the participants was 43 years. Nearly half of the sample had a diagnosis of pathology, with functional disorders being the most frequent laryngeal pathology. None of the demographic, behavioral, and occupational factors analyzed were statistically associated with laryngeal pathology. Although university teachers do not have an increased risk of laryngeal pathology, self-perceived voice disorders were more prevalent in teachers than in nonteachers. Vocal effort and the number of years teaching have a significant effect on voice disorders prevalence among teachers. CONCLUSIONS: Voice disorders have a higher rate of occurrence among university teachers. Demands of teaching, like vocal effort and years of teaching, and not other demographic and/or behavioral factors, are the risk factors that increase the rate of occurrence of voice disorders among the university teachers. Risk factors that predispose to laryngeal pathology were not detected in the present study. However, the high prevalence of functional laryngeal pathologies underlines the importance of further investigation toward this type of laryngeal pathology in this academic population.

Combining urban wastewater treatment with biohydrogen production--an integrated microalgae-based approach.

The aim of the present work was the simultaneous treatment of urban wastewater using microalgae and the energetic valorization of the obtained biomass. Chlorella vulgaris (Cv), Scenedesmus obliquus (Sc) and a naturally occurring algal Consortium C (ConsC) were grown in an urban wastewater. The nutrient removals were quite high and the treated water fits the legislation (PT Dec-Lei 236/98) in what concerns the parameters analysed (N, P, COD). After nutrient depletion the microalgae remained two more weeks in the photobioreactor (PBR) under nutritional stress conditions, to induce sugar accumulation (22-43%). The stressed biomass was converted into biohydrogen (bioH2), a clean energy carrier, through dark fermentation by a strain of the bacteria Enterobacter aerogenes. The fermentation kinetics were monitored and fitted to a modified Gompertz model. The highest bioH2 production yield was obtained for S. obliquus (56.8 mL H2/gVS) which was very similar when using the same algae grown in synthetic media.