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The mechanism of the metal centered reduction of metmyoglobin (MbFeIII) by sulfide species (H2S/HS-) under an argon atmosphere has been studied by a combination of spectroscopic, kinetic, and computational methods. Asymmetric S-shaped time-traces for the formation of MbFeII at varying ratios of excess sulfide were observed at pH 5.3 < pH < 8.0 and 25 °C, suggesting an autocatalytic reaction mechanism. An increased rate at more alkaline pHs points to HS- as relevant reactive species for the reduction. The formation of the sulfanyl radical (HS•) in the slow initial phase was assessed using the spin-trap phenyl N-tert-butyl nitrone. This radical initiates the formation of S-S reactive species as disulfanuidyl/ disulfanudi-idyl radical anions and disulfide (HSSH•-/HSS•2- and HSS-, respectively). The autocatalysis has been ascribed to HSS-, formed after HSSH•-/HSS•2- disproportionation, which behaves as a fast reductant toward the intermediate complex MbFeIII(HS-). We propose a reaction mechanism for the sulfide-mediated reduction of metmyoglobin where only ferric heme iron initiates the oxidation of sulfide species. Beside the chemical interest, this insight into the MbFeIII/sulfide reaction under an argon atmosphere is relevant for the interpretation of biochemical aspects of ectopic myoglobins found on hypoxic tissues toward reactive sulfur species.

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To evaluate the flexural strength (FS) and flexural modulus (FM) of a commercial 3Y-TZ0P ceramic after artificial aging and either without or with two application times of non-thermal plasma treatments (NTP). In addition, changes in crystalline phase transformation and surface nano-topography after NTP application, during different aging periods, were evaluated. Ninety 3Y-TZP bars (45x4x3 mm) were made for FS and FM testing, and assigned to nine groups (n=10): no NTP/no aging (Control); no NTP/4h aging; no NTP/30h aging; 10s NTP/no aging; 10s NTP/4h aging; 10s NTP/30h aging; 60s NTP/no aging; 60s NTP/4h aging and 60s NTP/30h aging. Artificial accelerated aging was simulated using an autoclave (134º C at 2 bar) for up to 30h. FS and FM were assessed using a universal testing machine and data analyzed using a ANOVA and Tukey test (α=0.05). The volume change in zirconia monoclinic phase (MPV) was evaluated using X-ray diffraction and surface nano-topography was assessed using atomic force microscopy (baseline until 30h-aging). NTP application did not influence the FS and FM of zirconia. Compared to the Control (no NTP/no aging), the FS of zirconia samples treated for 30 hours in autoclave ("no NTP/30h aging" group) increased. Artificial aging for 30 hours significantly increased the FM of zirconia, regardless of NTP application. MPV tended to increase following the increase in aging time, which might result in the surface irregularities observed at 30h-aging. NTP did not alter the zirconia properties tested, but 30h-aging can change the zirconia FS, FM and MPV.

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BACKGROUND: Open-angle glaucoma (OAG) is an important cause of blindness worldwide. Laser trabeculoplasty, a treatment modality, still does not have a clear position in the treatment sequence. OBJECTIVES: To assess the effects of laser trabeculoplasty for treating OAG and ocular hypertension (OHT) when compared to medication, glaucoma surgery or no intervention. We also wished to compare the effectiveness of different laser trabeculoplasty technologies for treating OAG and OHT. SEARCH METHODS: We searched the Cochrane Central Register of Controlled Trials (CENTRAL) (which contains the Cochrane Eyes and Vision Trials Register) (2021, Issue 10); Ovid MEDLINE; Ovid Embase; the ISRCTN registry; LILACS, ClinicalTrials.gov and the WHO ICTRP. The date of the search was 28 October 2021. We also contacted researchers in the field. SELECTION CRITERIA: We included randomised controlled trials (RCTs) comparing laser trabeculoplasty with no intervention, with medical treatment, or with surgery in people with OAG or OHT. We also included trials comparing different types of laser trabeculoplasty technologies. DATA COLLECTION AND ANALYSIS: We used standard methods expected by Cochrane. Two authors screened search results and extracted data independently. We considered the following outcomes at 24 months: failure to control intraocular pressure (IOP), failure to stabilise visual field progression, failure to stabilise optic neuropathy progression, adverse effects, quality of life, and costs. We graded the 'certainty' of the evidence using GRADE. MAIN RESULTS: We included 40 studies (5613 eyes of 4028 people) in this review. The majority of the studies were conducted in Europe and in the USA. Most of the studies were at risk of performance and/or detection bias as they were unmasked. None of the studies were judged as having low risk of bias for all domains. We did not identify any studies of laser trabeculoplasty alone versus no intervention. Laser trabeculoplasty versus medication Fourteen studies compared laser trabeculoplasty with medication in either people with primary OAG (7 studies) or primary or secondary OAG (7 studies); five of the 14 studies also included participants with OHT. Six studies used argon laser trabeculoplasty and eight studies used selective laser trabeculoplasty. There was considerable clinical and methodological diversity in these studies leading to statistical heterogeneity in results for the primary outcome "failure to control IOP" at 24 months.  Risk ratios (RRs) ranged from 0.43 in favour of laser trabeculoplasty to 1.87 in favour of medication (5 studies, I2 = 89%). Studies of argon laser compared with medication were more likely to show a beneficial effect compared with studies of selective laser (test for interaction P = 0.0001) but the argon laser studies were older and the medication comparator group in those studies may have been less effective. We considered this to be low-certainty evidence because the trials were at risk of bias (they were not masked) and there was unexplained heterogeneity. There was evidence from two studies (624 eyes) that argon laser treatment was associated with less failure to stabilise visual field progression compared with medication (7% versus 11%, RR 0.70, 95% CI 0.42 to 1.16) at 24 months and one further large recent study of selective laser also reported a reduced risk of failure at 48 months (17% versus 26%) RR 0.65, 95% CI 0.52 to 0.81, 1178 eyes). We judged this outcome as moderate-certainty evidence, downgrading for risk of bias. There was only very low-certainty evidence on optic neuropathy progression. Adverse effects were more commonly seen in the laser trabeculoplasty group including peripheral anterior synechiae (PAS) associated with argon laser (32% versus 26%, RR 11.74, 95% CI 5.94 to 23.22; 624 eyes; 2 RCTs; low-certainty evidence); 5% of participants treated with laser in three studies of selective laser group had early IOP spikes (moderate-certainty evidence). One UK-based study provided moderate-certainty evidence that laser trabeculoplasty was more cost-effective.  Laser trabeculoplasty versus trabeculectomy Three studies compared laser trabeculoplasty with trabeculectomy. All three studies enrolled participants with OAG (primary or secondary) and used argon laser. People receiving laser trabeculoplasty may have a higher risk of uncontrolled IOP at 24 months compared with people receiving trabeculectomy (16% versus 8%, RR 2.12, 95% CI 1.44 to 3.11; 901 eyes; 2 RCTs). We judged this to be low-certainty evidence because of risk of bias (trials were not masked) and there was inconsistency between the two trials (I2 = 68%). There was limited evidence on visual field progression suggesting a higher risk of failure with laser trabeculoplasty. There was no information on optic neuropathy progression, quality of life or costs. PAS formation and IOP spikes were not reported but in one study trabeculectomy was associated with an increased risk of cataract (RR 1.78, 95% CI 1.46 to 2.16) (very low-certainty evidence). AUTHORS' CONCLUSIONS: Laser trabeculoplasty may work better than topical medication in slowing down the progression of open-angle glaucoma (rate of visual field loss) and may be similar to modern eye drops in controlling eye pressure at a lower cost. It is not associated with serious unwanted effects, particularly for the newer types of trabeculoplasty, such as selective laser trabeculoplasty.

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OBJECTIVES: To evaluate the effect of argon plasma treatment (PLA) when combined with sandblasting (SAN), silanization (SIL), and hydrophobic bonding resin (HBR) on the shear bond strength (SBS) of a two-year water-aged resin composite bonded to a newly placed composite after 24 hours and one year of water-storage. METHODS AND MATERIALS: Thirty-six light-cured composite plates (20mm x 20mm x 4mm thick) were obtained and stored at 37°C in distilled water for 2 years. These aged plates were distributed into 6 groups (n=6) according to the surface treatment: no treatment (Negative Control); SAN+SIL+HBR (Positive Control); SAN+PLA+SIL+HBR; PLA+ SIL+HBR; PLA+SIL; PLA+HBR. Fresh resin composite cylinders were built up using silicone molds (hole: 1.5 mm high x 1.5 mm diameter) positioned over the aged plates. Half of the SBS samples were stored in distilled water for 24 hours and loaded until failure, while the other half were stored for 1 year before being tested. Data were submitted to two-way analysis of variance and post-hoc Tukey Test (preset alpha of 0.05). RESULTS: Positive Control, SAN+PLA+SIL+HBR and PLA+SIL+HBR groups presented higher SBS means at the 24 hour evaluation. After 1 year of water storage, all groups demonstrated significant SBS reduction, with the SAN+PLA+SIL+HBR group presenting the highest SBS. CONCLUSIONS: Resin plasma treatment in combination with other surface treatments can improve the SBS of composite repairs after one year of water storage. The SBS of the composite repair was not stable over time regardless of the surface treatment.

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The heating of a chromophore due to internal conversion and its cooling down due to energy dissipation to the solvent are crucial phenomena to characterize molecular photoprocesses. In this work, we simulated the ab initio nonadiabatic dynamics of cytosine, a prototypical chromophore undergoing ultrafast internal conversion, in three solvents-argon matrix, benzene, and water-spanning an extensive range of interactions. We implemented an analytical energy-transfer model to analyze these data and extract heating and cooling times. The model accounts for nonadiabatic effects, and excited- and ground-state energy transfer, and can analyze data from any dataset containing kinetic energy as a function of time. Cytosine heats up in the subpicosecond scale and cools down within 25, 4, and 1.3 ps in argon, benzene, and water, respectively. The time constants reveal that a significant fraction of the benzene and water heating occurs while cytosine is still electronically excited.

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The vertebrate fossil record of the Pampean Region of Argentina occupies an important place in South American vertebrate paleontology. An abundance of localities has long been the main basis for constructing the chronostratigraphical/geochronological scale for the late Neogene-Quaternary of South America, as well as for understanding major patterns of vertebrate evolution, including the Great American Biotic Interchange. However, few independently-derived dates are available for constraining this record. In this contribution, we present new 40Ar/39Ar dates on escorias (likely the product of meteoric impacts) from the Argentinean Atlantic coast and statistically-based biochronological analyses that help to calibrate Late Miocene-Pliocene Pampean faunal successions. For the type areas of the Montehermosan and Chapadmalalan Ages/Stages, our results delimit their age ranges to 4.7-3.7 Ma and ca. 3.74-3.04 Ma, respectively. Additionally, from Buenos Aires Province, dates of 5.17 Ma and 4.33 Ma were recovered for "Huayquerian" and Montehermosan faunas. This information helps to better calibrate important first appearances of allochthonous taxa in South America, including one of the oldest records for procyonids (7.24-5.95 Ma), cricetids (6.95-5.46 Ma), and tayassuids (> 3.74 Ma, oldest high-confidence record). These results also constrain to ca. 3 Ma the last appearances of the autochthonous sparassodonts, as well as terror birds of large/middle body size in South America. South American faunal turnover during the late Neogene, including Late Pliocene extinctions, is interpreted as a consequence of knock-on effects from global climatic changes and initiation of the icehouse climate regime.

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OBJECTIVES: To evaluate the effect of atmospheric pressure plasma (PLA), sandblasting (SAN), silanization (SIL) and hydrophobic bonding resin (HBR) on the micro-shear bond strength (MSBS) of fresh nanofilled (NF) or microhybrid (MH) composites to water-aged nanofilled composite. MATERIALS AND METHODS: NF plates were fabricated and stored in distilled water for 4 months. The aged plates were assigned to the groups (n = 6): 1- untreated; 2- SAN + SIL + HBR; 3- HBR; 4- PLA + HBR; 5- SAN + HBR; 6- SAN + PLA + HBR; and 7- PLA. Two fresh composite cylinders were constructed on each plate with NF or MH composites and tested after 24 h or 1 year of water-storage, using the MSBS testing. Data were analyzed by three-way ANOVA and Tukey test (α = 0.05). RESULTS: NF yielded better outcomes than MH at 24 h, which was not observed at 1 year. HBR showed the highest MSBS results, while untreated and PLA groups yielded the lowest one. MSBS reduced for all groups after 1 year. CONCLUSIONS: Only HBR can obtain good MSBS results, while PLA alone was not beneficial. After 1 year, a reduction in repair MSBS was observed and the type of composite did not influence the results. CLINICAL RELEVANCE: The repair technique can be simplified with the use of only an adhesive and macromechanical retentions in the old composite, regardless the type of fresh composite.

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STATEMENT OF PROBLEM: Nonthermal argon plasma (NTAP) has been reported to improve the bond strength of resin cements to yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) ceramics. However, the effect of the inevitable delay before cementation and after treating Y-TZP ceramics with NTAP is unclear. PURPOSE: The purpose of this in vitro study was to investigate whether delays of 8, 12, and 24 hours between the Y-TZP ceramic treatment with NTAP and the cementation would affect the surface energy and the bond strength of a self-adhesive resin cement to Y-TZP ceramic. MATERIAL AND METHODS: Sixty plates and 50 blocks of 3Y-TZP ceramic were divided into 2 groups (n=30 and n=25): as-sintered (AS) and airborne-particle abraded with 50-µm Al2O3 (APA). These groups were further divided into 5 subgroups (n=6 and n=5) according to the delay between the NTAP treatment and the measurement of surface energy and microtensile bond strength (µTBS) evaluation: (0, 8, 12, and 24 hours). For both 3Y-TZP surface conditions (AS and APA), a control group without NTAP treatment was used (ASC and APAC). The surface energy (SE) was evaluated with a goniometer and the 3Y-TZP elemental composition with X-ray photoelectron spectroscopy (XPS). For the µTBS test, the 3Y-TZP ceramic blocks were cemented to composite resin blocks with a self-adhesive resin cement. After storage in distilled water at 37 °C for 24 hours, the 3Y-TZP-composite resin blocks were sectioned into beams and submitted to a µTBS test. Data were submitted to 2-way ANOVA and the Tukey HSD test (α=.05). RESULTS: For the AS group, NTAP increased the SE irrespective of the delay before measurement: ASC<0 hour=8 hours=12 hours=24 hours (P<.05). For the APA group, except after 12 hours, NTAP also increased the surface energy (P<.05). XPS analysis showed an increase in the oxygen/carbon ratio after NTAP treatment for both groups. For the AS group, NTAP increased the µTBS after 0, 8, and 12 hours (P<.05), whereas for the APA group this occurred only after 8 hours (P<.05). For the AS and APA groups, the highest µTBS was reached after 8 hours (P<.05). CONCLUSIONS: Treatment of 3Y-TZP ceramic with NTAP improved the SE and increased the µTBS of self-adhesive resin cement to 3Y-TZP ceramic. These effects were time dependent, with better results at 8 hours after NTAP treatment.

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The present study aimed to demonstrate the possibility to treat corneal neovascularization using the combination of anti-VEGF injection and argon laser photocoagulation.

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RESUMEN Presentamos el caso de un paciente con foseta del disco óptico, quien presentó una disminución de la agudeza visual secundaria a desprendimiento seroso de retina. Se decidió realizar una inyección intravítrea de 0.3ml de gas C3F8 (100%), seguida de fotocoagulación con láser de argón en el borde temporal de la foseta, logrando reaplicación total de la retina, con reabsorción de todo el líquido subretiniano visible en la tomografía de coherencia optica (OCT) luego de 400 días. Además hubo una mejoría significativa en la agudeza visual.

ABSTRACT We present the case of a patient with an optic disk pit, presenting with great loss of visual acuity secondary to serous retinal detachment. The management chosen was an intravitreal injection of 0.3 mL of C3F8 (100%), followed by argon laser photocoagulation on the temporal edge of the pit, ), achieving total retinal reattachment , and reabsorption of all subretinal fluid visible at optical coherence tomography after 400 days, in addition to great improvement in visual acuity.

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