Solar Gas-Phase CO2 Hydrogenation by Multifunctional UiO-66 Photocatalysts.

Solar-assisted CO2 conversion into fuels and chemical products involves a range of technologies aimed at driving industrial decarbonization methods. In this work, we report on the development of a series of multifunctional metal-organic frameworks (MOFs) based on nitro- or amino-functionalized UiO-66(M) (M: Zr or Zr/Ti) supported RuOx NPs as photocatalysts, having different energy band level diagrams, for CO2 hydrogenation under simulated concentrated sunlight irradiation. RuOx(1 wt %; 2.2 ± 0.9 nm)@UiO-66(Zr/Ti)-NO2 was found to be a reusable photocatalyst, to be selective for CO2 methanation (5.03 mmol g-1 after 22 h;, apparent quantum yield at 350, 400, and 600 nm of 1.67, 0.25, and 0.01%, respectively), and to show about 3-6 times activity compared with previous investigations. The photocatalysts were characterized by advanced spectroscopic techniques like femto- and nanosecond transient absorption, spin electron resonance, and photoluminescence spectroscopies together with (photo)electrochemical measurements. The photocatalytic CO2 methanation mechanism was assessed by operando FTIR spectroscopy. The results indicate that the most active photocatalyst operates under a dual photochemical and photothermal mechanism. This investigation shows the potential of multifunctional MOFs as photocatalysts for solar-driven CO2 recycling.

Reference values and reliability of occlusal force distribution and occlusal time measured by the T-Scan system in adults with healthy dentition.

PURPOSE: Reference values of occlusal characteristics are needed to interpret the data obtained using the T-Scan System. This study aimed to establish reference values for and to assess the reliability of, occlusal force distribution in the maximal intercuspal position and the occlusion time in young adults with healthy dentition. MATERIALS AND METHODS: In total 178 adults with natural dentition participated in this retrospective cross-sectional study, of whom 76 performed a retest session. Several occlusal recordings were obtained from each participant using the T-Scan system while asking them to bite two or three consecutive times (multi-bite) or only once (single-bite) at the maximal intercuspal position. The lateral and anteroposterior occlusal force distribution were determined as percentages in the right and posterior teeth . Occlusion time was measured in seconds. After the occlusal force distribution and occlusion time percentiles were calculated, reliability was assessed by the intraclass correlation coefficient. RESULTS: The 5th-95th percentiles for occlusal force distribution were 34%-67% on the right teeth and 55%-94% on the posterior teeth. The 90th percentile for multi-bite occlusion time was 0.17 s and for single-bite occlusion time was 0.27 s. The intraclass correlation coefficients for lateral occlusal force distribution, anteroposterior occlusal force distribution, multi-bite occlusion time, and single-bite occlusion time were 0.70, 0.68, 0.58, and 0.67, respectively. CONCLUSIONS: This study generated reference values for key occlusal characteristics (occlusal force distribution and occlusion time) when using the T-Scan system. These values showed moderate reliability.

Photodynamics of azaindoles in polar media: the influence of the environment.

We have studied the relaxation dynamics of a family of azaindole (AI) structural isomers, 4-, 5-, 6- and 7-AI, by steady-state and time-resolved methods (fs-transient absorption and fluorescence up-conversion), in solvents of different polarity. The measurements in aprotic solvents show distinctive fluorescence yields and excited state lifetimes among the isomers, which are tuned by the polarity of the medium. Guided by simple TD-DFT calculations and based on the behavior observed in the isolated species, it has been possible to address the influence of the environment polarity on the relaxation route. According to the obtained picture, the energy of the nπ* state, which is strongly dependent on the position of the pyridinic nitrogen, controls the rate of the internal conversion channel that accounts for the distinctive photophysical behavior of the isomers. On the other hand, preliminary measurements in protic media (methanol) show a very different photodynamical behavior, in which the anomalous measured fluorescent patterns are very likely the result of reactive channels (proton transfer) triggered by the electronic excitation.

Accuracy of digital and conventional systems in locating occlusal contacts: A clinical study.

STATEMENT OF PROBLEM: The accuracy of methods used for locating occlusal contacts throughout the entire clinical procedure has been poorly studied. PURPOSE: The purpose of this clinical study was to determine the reproducibility and criterion validity for different methods of locating occlusal contacts. MATERIAL AND METHODS: Thirty-two adults with natural dentitions participated in this cross-sectional test-retest study. In total, occlusal contacts at maximum intercuspation were recorded by using 15 methods: silicone transillumination with Occlufast Rock (40, 50, 100, and 200 µm) and Occlufast CAD (40 and 50 µm); virtual occlusion (100, 200, 300, and 400 µm); articulating film (12-, 40-, 100-, and 200-µm-thick); and T-Scan III. Images of the occlusal records were scaled and calibrated spatially, and the occlusal contacts of the right posterior mandibular teeth were delimited by using the FIJI software program. Reproducibility was expressed as 95% confidence intervals (95% CI) of the percentage of agreement in the location of the occlusal contacts between images from the test sessions against retest sessions using the same method. Criterion validity was expressed as 95% CI of the percentage of agreement in the location of the occlusal contacts between images from the test sessions against images from Occlufast Rock (criterion standard). RESULTS: Occlufast Rock achieved 85% to 95% agreement in the location of the occlusal contacts between the 2 sessions, whereas Occlufast CAD, 200-µm articulating film, and T-Scan offered 79% to 86%, 68% to 75%, and 65% to 75% agreement, respectively. The most valid method was Occlufast CAD (74% to 80%) followed by the 200-µm articulating film (57% to 63%), 400-µm virtual occlusion (53% to 62%), 100-µm articulating film (52% to 60%), and T-Scan (48% to 56%). CONCLUSIONS: Conventional methods, such as 100- and 200-µm articulating film and digital methods, including 400 µm virtual occlusion and T-Scan, offer sufficient accuracy in locating the occlusal contacts. However, strategies are needed to improve accuracy.

Early Loading of Two Implants Supporting Mandibular Overdentures in Geriatric Edentulous Patients: A 12-Year Follow-Up Study.

Background: This study aims to show the clinical outcomes of implants supporting mandibular overdentures in edentulous patients. Methods: Mandibular edentulous patients were diagnosed with an oral examination, panoramic radiograph, and diagnostic casts for intermaxillary relations and treated with overdentures over two implants. After two-stage surgery, implants were early loaded with an overdenture at 6 weeks. Results: Fifty-four patients (28 females and 24 males) were treated with 108 implants. Thirty-two patients (59.2%) had a previous history of periodontitis. Twenty-three patients (46%) were smokers. Forty patients (74.1%) suffered from systemic diseases (i.e., diabetes, cardiovascular diseases). The clinical follow-up of the study was 147.8 ± 10.4 months. The clinical outcomes showed a global success of 94.5% of implants. Fifty-four overdentures were placed in the patients over the implants. The mean marginal bone loss was 1.12 ± 0.34 mm. Nineteen patients (35.2%) showed some kind of mechanical prosthodontic complication. Sixteen implants (14.8%) were associated with peri-implantitis. Conclusions: Based on the clinical results obtained, we can determine that the treatment of elderly edentulous patients with mandibular overdentures through the early loading of two placed implants is a successful implant protocol.

Influence of H-bonds on the photoionization of aromatic chromophores in water: The aniline molecule.

We have conducted time-resolved experiments (pump-probe and pump-repump-probe) on a model aromatic chromophore, aniline, after excitation in water at 267 nm. In the initial spectra recorded, in addition to the absorption corresponding to the bright ππ* excitation, the fingerprint of a transient state with the electron located on the solvent molecule is identified. We postulate that the latter corresponds to the πσ* state along the N-H bond, whose complete relaxation with a ∼500 ps lifetime results in the formation of the fully solvated electron and cation. This ionization process occurs in parallel with the ππ* photophysical channel that yields the characteristic ∼1 ns fluorescence lifetime. The observed branched pathway is rationalized in terms of the different H-bonds that the water establishes with the amino group. The proposed mechanism could be common for aromatics in water containing N-H or O-H bonds and would allow the formation of separated charges after excitation at the threshold of their electronic absorptions.

Halogen-free photosensitizers based on meso-enamine-BODIPYs for bioimaging and photodynamic therapy.

The search for efficient heavy atom free photosensitizers (PSs) for photodynamic therapy (PDT) is a very active field. We describe herein a simple and easily accessible molecular design based on the attachment of an enamine group as an electron-donor moiety at the meso position of the BODIPY core with different alkylation patterns. The effect of the alkylation degree and solvent polarity on the photophysical properties in terms of splitting absorption bands, fluorescence efficiencies and singlet oxygen production is analyzed in depth experimentally using spectroscopic techniques, including femtosecond and nanosecond transient absorption (fs- and ns-TA) and using computational simulations based on time-dependent density functional theory. The correlation between the theoretical/experimental results permits the rationalization of the observed photophysical behavior exhibited by meso-enamine-BODIPY compounds and the determination of mechanistic details, which rule the population of the triplet state manifold. The potential applicability as a theragnostic agent for the most promising compound is demonstrated through in vitro assays in HeLa cells by analyzing the internalization, localization and phototoxic action.

Regio- and Stereoselective 1,2-Oxyhalogenation of Non-Conjugated Alkynes via Directed Nucleopalladation: Catalytic Access to Tetrasubstituted Alkenes.

A catalytic 1,2-oxyhalogenation method that converts non-conjugated internal alkynes into tetrasubstituted alkenes with high regio- and stereoselectivity is described. Mechanistically, the reaction involves a PdII /PdIV catalytic cycle that begins with a directed oxypalladation step. The origin of regioselectivity is the preference for formation of a six-membered palladacycle intermediate, which is facilitated by an N,N-bidentate 2-(pyridin-2-yl)isopropyl (PIP) amide directing group. Selectivity for C(alkenyl)-X versus -N (X=halide) reductive elimination from the PdIV center depends on the identity of the halide anion; bromide and iodide engage in C(alkenyl)-X formation, while intramolecular C(alkenyl)-N reductive elimination occurs with chloride to furnish a lactam product. DFT calculations shed light on the origins of this phenomenon.

The Role of Manganese in Very Low Birth Weight Infants.

OBJECTIVES: High manganese (Mn) levels during fetal growth or prolonged parenteral nutrition (PN) may have adverse effects on neurodevelopment. We aim to report on Mn levels and their short-term impact on clinical course in very low birth weight infants. METHODS: An observational study including newborns with a gestational age (GA) ≤32 weeks and/or ≤1500 g of birth weight (BW). Newborns received intravenous supplementation of Mn at 1 µg/kg/day (Peditrace ® ) in PN and continued with fortified breast milk. Mothers answered surveys about dietary and other habits and blood levels of Mn in newborns were analyzed at days 1, 15, and 30 of life. Associations of Mn levels with mothers' and newborns' data were evaluated and adjusted for multiple comparisons. RESULTS: One hundred and sixty premature infants were recruited. Median blood Mn levels at birth were 43.0 and 24.5 µg/L at day 30. No important association with mothers' data was found. Median [interquartile range (IQR)] duration of PN was 8 days (7-14). A prolonged PN and late oral feeding showed a nonsignificant association with lower blood Mn levels at day 30 ( P = 0.010, P threshold 0.003). Mn levels at day 15 and 30 were associated with increasing GA ( P < 0.001). Low Mn was not a significant predictor of adverse outcomes such as retinopathy of prematurity, bronchopulmonary dysplasia, or respiratory distress syndrome after adjusting for potential confounders and multiple testing. CONCLUSIONS: Mn showed lower levels with decreasing GA and prolonged PN. Using a low Mn PN solution may not raise blood Mn levels in premature infants.

Marginal Bone Loss in Internal Conical Connection Implants Placed at the Crestal and Subcrestal Levels before Prosthetic Loading: A Randomized Clinical Study.

The vertical position concerning the bone in which the implants are placed has been related as one of the factors causing marginal bone loss. The objective of this study was to evaluate the bone loss that occurs before prosthetic loading around tapered internal connection (CIC) implants placed at the crestal (C) and subcrestal (S) levels. METHOD: A randomized clinical trial (RCT) was carried out, with a sample size of 62 implants placed in 27 patients who underwent radiological controls on the day of placement, at one month, and at 4 months, and stability was measured by resonance frequency analysis (RFA) on three occasions. RESULTS: Bone loss in implants C and S from the time of placement (T0) and the month after (T1) was not significant (p = 0.54) (C = 0.19 mm and S = 0.15 mm). The difference between one month (T1) and four months (T2) (C = 0.17 mm and S = 0.22 mm) was not significant either (p = 0.26). The difference between the day of placement (T0) and the third and last measurement (T2) was almost null (p = 0.94) (C = 0.35 mm and S = 0.36). The overall success rate of the implants was 97.8%. The stability of the implants measured with RFA went from 70.60 (T0) to 73.16 (T1) and 74.52 (T2). CONCLUSIONS: No significant differences were found in the bone loss for implants placed at the C and S levels. The millimeters of bone loss detected in both vertical positions did not have a significant impact on the stability of the implants.

PdII -Catalyzed C(alkenyl)-H Activation Facilitated by a Transient Directing Group.

Palladium(II)-catalyzed C(alkenyl)-H alkenylation enabled by a transient directing group (TDG) strategy is described. The dual catalytic process takes advantage of reversible condensation between an alkenyl aldehyde substrate and an amino acid TDG to facilitate coordination of the metal catalyst and subsequent C(alkenyl)-H activation by a tailored carboxylate base. The resulting palladacycle then engages an acceptor alkene, furnishing a 1,3-diene with high regio- and E/Z-selectivity. The reaction enables the synthesis of enantioenriched atropoisomeric 2-aryl-substituted 1,3-dienes, which have seldom been examined in previous literature. Catalytically relevant alkenyl palladacycles were synthesized and characterized by X-ray crystallography, and the energy profiles of the C(alkenyl)-H activation step and the stereoinduction model were elucidated by density functional theory (DFT) calculations.

Antibiotic Prescribing in Children Hospitalized With COVID-19 and Multisystem Inflammatory Syndrome in Spain: Prevalence, Trends, and Associated Factors.

The SARS-CoV-2 pandemic has caused an increase in antibiotic use in different settings. We describe the antibiotic prescribing prevalence, associated factors and trends, as well as concomitant bacterial infections in children hospitalized with COVID-19 or multisystemic inflammatory syndrome related to SARS-CoV-2 in Spain.

Fiber laser system of 1550 nm femtosecond pulses with configurable properties for the two-photon excitation of transient currents in semiconductor detectors.

A fiber laser system emitting ultrashort femtosecond pulses at 1550 nm with configurable properties has been developed as an excitation source for the two-photon absorption transient current technique (TPA-TCT). The modules of the system are designed to provide the optical specifications required at the output for localized characterization of semiconductor radiation detectors: variation of pulse energy between 10 nJ and 10p J, variation of the pulse repetition rate from 8.2 MHz to single shot, and variation of pulse duration between 300 and 600 fs. The validity of the system as an excitation source in the TPA-TCT is demonstrated by measuring spatially resolved excited charge carriers in a silicon detector.

Variation in Dental Occlusal Schemes Two Years After Placement of Single-Implant Posterior Crowns: A Preliminary Study.

Some authors have recommended that implant-supported single crowns should only contact during heavy clenching. However, a lack of occlusal contact with moderate clenching may cause supraeruption of antagonist natural teeth. The main objective of this study was to assess changes in the occlusal contacts of posterior implant-supported single crowns with natural antagonist teeth 2 years after placement. The occlusal schemes of 14 patients who received 16 implant-supported single crowns in molar and premolar regions were assessed in this prospective study. Just after crown placement, at 6 months and after 2 years, a silicone maxillomandibular relationship and T-scan records were obtained during the intercuspal position with light and heavy clenching, determined using near half of the maximum force and maximum force, respectively. Occlusal contacts were assessed quantitatively and qualitatively in the implant-supported single crowns, contralateral tooth, and adjacent tooth; the latter 2 were used as controls. After 6 months and 2 years, no significant variations were observed in any region of the occlusal scheme in any assessments, including silicone record or T-Scan, using light or heavy clenching, and qualitative or quantitative occlusal contact assessment. In this preliminary study, the occlusal scheme did not vary at the intercuspal position 2 years after placing posterior implant-supported single crowns.

Low-Valent Tungsten Catalysis Enables Site-Selective Isomerization-Hydroboration of Unactivated Alkenes.

A tungsten-catalyzed hydroboration of unactivated alkenes at distal C(sp3)-H bonds aided by native directing groups is described herein. The method is characterized by its simplicity, exquisite regio- and chemoselectivity, and wide substrate scope, offering a complementary site-selectivity pattern to other metal-catalyzed borylation reactions and chain-walking protocols.

USE OF LOCAL ANESTHETICS WITH A VASOCONSTRICTOR AGENT DURING DENTAL TREATMENT IN HYPERTENSIVE AND CORONARY DISEASE PATIENTS. A SYSTEMATIC REVIEW.

BACKGROUND: Coronary disease and Hypertension are highly prevalent health problems worldwide, with the latter being one of the most common diseases in patients visiting dental clinics. Local anesthetics (LAs) with vasoconstrictor agents (VC) are known to be commonly used in dental practice. For the above-mentioned reasons, dentists should know how to adapt and treat patients with these hazardous conditions. OBJECTIVE: The aim of this study was to find out if the use of local anesthetics (LAs) in combination with vasoconstrictor (VC) agents in dental treatment presents a risk in patient with a known history of Hypertension and/or Coronary disease. MATERIALS AND METHODS: This systematic review was conducted in accordance with The PRISMA guidelines and registered on the PROSPERO database (CRD42020187369). The search strategy was based on Mesh terms, Boolean operator AND, and the PICO model. It was designed to identify all the randomized clinical trials (RCTs) published in the last 30 years, which assessed whether the use of LA with VC agents in dental treatment produces a significant increase/decrease in hemodynamics in patients with known history of Hypertension and/or Coronary disease. The Cochrane Collaboration's tool was used to assess risk of bias of the included RCTs. RESULTS: An initial electronic search resulted in 87 papers; however only 9 RCTs met the inclusion criteria. There was a total of 482 subjects (N = 482), of which 412 had a known history of Hypertension or Coronary disease. CONCLUSIONS: According to the literature reviewed, the use of 1 to 2 cartridges of local anesthetics with 1:80,000, 1:100,000 or 1:200,000 epinephrine in patients with controlled Hypertension and/ or Coronary disease is safe. Randomized clinical trials are essential in determining the safety or risks associated with the use of LAs with VC agents in patients with poorly controlled Hypertension and Coronary disease.

Revisiting the Spectroscopy of Water Dimer in Jets.

Laser spectroscopy in jets is one of the main sources of structural data from molecular aggregates. Consequently, numerous and sophisticated experimental systems have been developed to extract precise information, which is usually interpreted in the light of quantum mechanical calculations. However, even with the most sophisticated experiments, it is sometimes difficult to interpret the experimental results. We present here the example of water dimer and how after almost 70 years, the assignment of its mass-resolved IR spectrum still generates controversy that extends toward the mechanism of ionization of water aggregates.

Masticatory rhythm 3 months after treatment with unilateral implant-supported fixed partial prosthesis: A clinical study.

STATEMENT OF PROBLEM: Whether treatment with an implant-supported fixed partial prosthesis (ISFPP) affects the masticatory rhythm in patients with unilateral posterior missing teeth is unclear. PURPOSE: The purpose of this prospective clinical study was to determine the change in masticatory rhythm in participants with unilateral posterior missing teeth 3 months after treatment with an ISFPP and to assess whether treatment influenced the stability of the masticatory rhythm. MATERIAL AND METHODS: Thirty participants (mean age 59 years; 17 women) with unilateral posterior missing teeth were treated with 1-, 2-, or 3-unit ISFPPs. Ten healthy individuals (mean age 36 years; 8 women) with a complete natural dentition were included in a control group. In this prospective study, each participant performed 3 masticatory assays (freestyle, unilateral right, and unilateral left) at baseline and at the 3-month follow-up. Each assay comprised 5 trials of 20 cycles masticating pieces of silicone placed in a latex bag. The time needed to complete the 20 masticatory cycles per trial was measured, and the mean masticatory frequency was calculated for each assay. Coefficients of variation were then calculated from the 5 mean values of the masticatory trials. Differences in the data at 3 months and baseline were analyzed by using the Wilcoxon or paired t tests. The control and treated groups were compared by analysis of variance or Mann-Whitney U tests (α=.05). RESULTS: After 3 months, participants treated with ISFPPs showed an increase of 8.7% in masticatory frequency during freestyle mastication (P<.001) and an 8.0% increase during unilateral mastication on the treated side (P<.01). At baseline, the coefficient of variation of masticatory frequency on the treated side was higher in the ISFPP group than in the control group during unilateral mastication (P=.033). Three months after treatment, there was a significant reduction in the coefficient of variation during unilateral mastication on the treated side of the ISFPP group (P<.001). The treatment group also reached a masticatory frequency similar to that of the control group (75 and 78 cycles per minute, respectively). CONCLUSIONS: Treatment with ISFPPs accelerated the masticatory rhythm of individuals with unilateral posterior missing teeth, who achieve similar rhythms to those with complete natural dentitions. The stability of the masticatory rhythm was also restored, indicating an improvement in masticatory function.

Evaluation of the quality of life and satisfaction in patients using complete dentures versus mandibular overdentures. Systematic review and meta-analysis.

BACKGROUND: The World Health Organization (WHO) recognizes edentulism as a physical impairment that results in a negative impact in the daily activities. OBJECTIVE: The study aimed to compare the satisfaction and the quality of life, in patients treated with implant retained overdentures with two mandibular implants (IOD) against those with mandibular conventional complete dentures (CCD). METHODS: Different search strategies were used to screen for articles in Pubmed/Medline, Cochrane Library and Scielo of the last 17 years (2003-2020). The keywords used were: "quality of life OR satisfaction" AND "complete denture OR conventional denture" AND "overdenture OR implant retained." RESULTS: Six articles and two more were added by manual search. The population was 400 in the CCD and 412 for IOD. The mean age was 64.3 ± 6.41 years. The group was comprised of 283 men and 427 women. The scores obtained in the visual analog scale (VAS) before and after the treatment were statistically significant in favor of the IOD for overall satisfaction, (WMD: 12.329; 95% CI: 4.873 to 19.784, p-value = 0.001), comfort, speech and stability. For esthetics and chewing there was non-significant improvement while hygiene worsened for the IOD. For the comparison after the treatment between both treatment modalities a statistically significant improvement was found in overall satisfaction (WMD: 14.408; 95% CI: 8.589 to 20.226, p-value < 0.001), comfort, speech, chewing and stability in favor of the IOD but not in esthetics or hygiene. CONCLUSIONS: This systematic review and meta-analysis show the superiority of the IOD, despite is not achieved in all aspects.