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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

An nπ* gated decay mediates excited-state lifetimes of isolated azaindoles.

Aiming to serve as a guide to understand the relaxation mechanisms of more complex aza-aromatic compounds, such as purine bases, we have studied the non-radiative channels of a set of azaindole structural isomers: 4-, 5-, 6- and 7-azaindole (AI). The relaxation of the isolated molecules, after excitation at the low energy portion of their spectra, has been tracked by femtosecond time-resolved ionization, and the decay paths have been obtained with MS-CASPT2//TD-DFT calculations. Although the ultrashort measured lifetimes for 5- and 6-AI are in contrast to the long-living excited state found in 7-AI, the calculations describe a common relaxation pathway. Along it, the initially excited ππ* states decay to the ground state through a conical intersection accessed through an nπ* state that functions as a gate state. The work reveals that the position of the nitrogen atoms in the purine ring determines the barrier to access the gate state and therefore, the rate of the non-radiative relaxation.

Changes in masticatory laterality 3 months after treatment with unilateral implant-supported fixed partial prosthesis.

OBJECTIVE: This study assessed changes in masticatory laterality in patients with unilateral posterior missing teeth 3 months after treatment with an implant-supported fixed partial prosthesis (ISFPP). METHODS: Thirty patients with unilateral posterior missing teeth participated in this prospective study. They were treated with one-, two- or three-unit ISFPPs. The control group comprised 10 healthy individuals with complete natural dentition. Each participant performed masticatory assays at baseline and at 3-month follow-up, chewing pieces of silicon inside a latex bag. Masticatory laterality was determined using three different methods: assessment of the first chewing cycle, of all cycles and application of a visual analogue scale. Data were compared using the Kruskal-Wallis or the Mann-Whitney U test as appropriate. RESULTS: Three months after treatment, a significant change in the asymmetry index towards the treated side and a significant reduction in the Unilateral Chewing Index were observed in the ISFPP group. No significant differences in masticatory laterality between groups were detected at 3-month follow-up, regardless of the method assessed. CONCLUSION: Treatment with ISFPPs alters the masticatory laterality, moving it to the treated side and increasing the degree of bilateral chewing in patients with unilateral posterior missing teeth.

Reliability and Validity of T-scan and 3D Intraoral Scanning for Measuring the Occlusal Contact Area.

PURPOSE: To determine the reliability of T-scan and 3D intraoral scan techniques for assessing the occlusal contact area (OCA), compared to occlusal registration and also to assess the validity of the techniques. MATERIALS AND METHODS: Thirty-one dentate adults participated in this cross-sectional study. T-scan records were used to measure the OCA at maximum bite force and at 50% of maximum force using the software's bite force selection tool. A second method measured the OCA between 2 virtual models scanned intraorally using a 3D surface scan and considering the occlusal contact at 2 interocclusal distances (0-100 and 0-200 µm). The third method measured OCA using occlusal registration at moderate and maximum occlusal force, and considering contact at the 2 interocclusal distances (0-100 and 0-200 µm). Images obtained using the 3 methods were analyzed using ImageJ software. Test-retest reliability was assessed by the intraclass correlation coefficient (ICC) and validity by Pearson correlations. RESULTS: ICCs ranged from 0.56 to 0.79 (p < 0.001) for the T-scan; 0.37 to 0.61 (p < 0.05) for 3D surface scan; and 0.92 to 0.95 (p < 0.0005) for occlusal registration. The highest OCA values were obtained using the T-scan, and the lowest using the 3D surface scan. Occlusal registration measurements had the highest correlations with those of the other techniques. CONCLUSIONS: T-scan is a reliable method for measuring the OCA, but the 3D surface scan is not. Occlusal registration showed a high validity.

Photophysical characterization of new and efficient synthetic sunscreens.

The photoprotective capabilities of a family of compounds have been investigated. Their relaxation mechanisms have been explored by fluorescence and transient absorption measurements, and the minimum energy relaxation pathways were modeled by CASSCF/CASPT2 methods. This study demonstrates their excellent properties as sunscreens, and provides novel mechanistic insights for the rational design of new species.

Excited state dynamics of aniline homoclusters.

We have investigated the relaxation, following excitation in the 290-235 nm region, of neutral aniline homoclusters (An)n formed in a supersonic expansion by femtosecond time resolved ionization. The applied method permits isolation of the dynamics of the dimer from that originated in bigger species of the generated distribution. Interestingly, and differently from the monomer and (An)n≥3 clusters, the dimer does not present a N-H dissociative 1πσ* channel. This fact can be explained in terms of the symmetric structure adopted, in which each molecule establishes two N-Hπ interactions, destabilizing the H dissociation channel. The observations permit relating the photophysics to the interactions established by the aniline units and confirming previous observations and theoretical predictions on the structure of aniline aggregates.

Methylthio BODIPY as a standard triplet photosensitizer for singlet oxygen production: a photophysical study.

A complete photophysical study on the iodinated-BODIPY, 3,5-dimethyl-2,6-diiodo-8-thiomethyl-pyrromethene (MeSBDP), demonstrated that it is an excellent triplet photosensitizer for singlet oxygen production in a broad range of apolar and polar solvents. Besides its absorption and fluorescence emission spectra, the dynamics of its excited states including its intersystem crossing rate was characterized by femtosecond transient experiments. The photophysical study of its triplet state by nanosecond transient absorption spectroscopy and phosphorescence emission concluded to a diffusion-controlled quenching of 3MeSBDP by O2 and to a fraction of triplet state quenching by O2 close to unity. The high (>0.87) and solvent-insensitive singlet oxygen quantum yield φΔ measured by singlet oxygen phosphorescence emission, together with the noticeable photostability of MeSBSP, as well as the absence of quenching of singlet oxygen by MeSBDP itself, allows claiming it as an alternative standard photosensitizer for singlet oxygen production, under excitation either in the UV or in the visible range.

Dynamics of Pyrroles Excited to the 3s/πσ* State.

The available experimental data provided by ultrafast dynamics studies of pyrrole and its derivatives in excited states of mixed Rydberg/valence 3s/πσ* character are strongly affected by the interaction with the laser pulses. Understanding these data has constituted an endeavor for several groups during the past few years. Here we apply a simple theoretical model that, including the interaction with the laser pulses, allows one to clarify some aspects of the discrepancies between measurements monitoring different experimental observables. New experimental data on pyrrole, 2,4-dimethylpyrrole, and 2,5-dimethylpyrrole are also provided to check the validity of the model and to gain more insight into the excited state dynamics of pyrrole systems.

Do implant-supported fixed partial prostheses improve masticatory performance in patients with unilateral posterior missing teeth?

OBJECTIVES: The purpose of this study was to determine the improvement in masticatory performance and satisfaction with chewing ability in partially edentulous patients after treatment with an implant-supported fixed partial prosthesis (ISFPP). MATERIAL AND METHODS: This prospective study included 30 patients (mean age 59 years; 17 women) with unilateral posterior missing teeth treated with one-, two- or three-unit ISFPPs and 10 healthy individuals (mean age 36 years; 8 women) with complete natural dentition to establish the normal levels of mastication. Three variables were determined at baseline and at 3-months' follow-up in all participants: masticatory performance according to the median particle size (MPS) during freestyle mastication and unilateral mastication on each side, and satisfaction with chewing ability using a visual analog scale. Paired samples t test and Kruskal-Wallis test were used for intra-group and inter-group comparisons. RESULTS: The MPS following freestyle mastication decreased significantly at 3 months in both groups. Significant reductions of 21%, 30%, and 42% in the MPS were obtained from unilateral mastication on the treated side after treatment with 1, 2, or 3 restorative units, respectively. Three months after ISFPP, satisfaction with chewing ability improved by 40% in the treatment group. CONCLUSIONS: Freestyle masticatory performance may improve slightly within three months of treatment with an ISFPP and may be similar to that of subjects with complete natural dentition. Patients may obtain a 21%-38% improvement in unilateral mastication on the treated side and a 26%-54% improvement in satisfaction with chewing ability.