Comparison of preemptive etoricoxib and dexamethasone in third molar surgery - a randomized controlled clinical trial of patient-reported and clinical outcomes.

OBJECTIVES: To compare preemptive single-dose etoricoxib and dexamethasone on postoperative patient satisfaction (pPS) and clinical parameters following the impacted mandibular third molar (IMTM) extraction. MATERIALS AND METHODS: A parallel-group, triple-blinded, controlled clinical study included a total of 90 patients (n = 30), randomized to receive: etoricoxib 90 mg, dexamethasone 4 mg, or no premedication (control group) 1 h before surgery. Paracetamol 500 mg was prescribed as rescue medication (RM). Check-ups were scheduled at 24 h, 48 h, and day 7 post-surgery. At each time point, pPS was assessed using the 5-point Likert scale. RM parameters, swelling, trismus, and the occurrence of adverse events were also recorded, and patients were instructed to rate the perceived pain on Visual Analogue Scale. RESULTS: In all the follow-up periods, data indicated significantly higher pPS scores in the preemptive medication groups when compared to the control group (p < 0.05). Both regimens delayed the first RM intake when compared to controls. In the etoricoxib group, a significantly lower total RM consumption was observed (p < 0.05). Dexamethasone significantly decreased swelling at each check-up and increased mouth opening at day 7 after the surgery (p < 0.05). CONCLUSIONS: Preemptive etoricoxib and dexamethasone elevate pPS after IMTM surgery. Etoricoxib improves RM parameters, while dexamethasone ameliorates the patient's postoperative functional ability. CLINICAL RELEVANCE: Preemptive etoricoxib and dexamethasone use may decrease patients' discomfort following the impacted mandibular third molar extraction. TRIAL REGISTRATION: ClinicalTrials.gov Identifier: NCT05791721. Date of Registration: 28/03/2023 (retrospectively registered).

Identification of Synthetic Organic Pigments (SOPs) Used in Modern Artist's Paints with Secondary Ion Mass Spectrometry with MeV Ions.

This work reports on the first systematic study using secondary ion mass spectrometry with MeV ions (MeV-SIMS) for analysis of synthetic organic pigments (SOPs) that can be usually found in modern and contemporary art paints. In order to prove the applicability of the method to different chemical classes of SOPs, 17 pigments were selected for the analyses. The focus was on blue and green phthalocyanines, yellow and red (naphthol AS) azo pigments, red quinacridone, anthraquinone, and diketopyrrolo-pyrrole pigments. Since there are no reference spectra available for this technique, pure pigment powders were measured first to create a database. Simple two-component paint systems were also prepared for testing purposes by mixing synthetic organic pigments with alkyd and acrylic binders. Commercial paints that contain the SOPs with identical C.I. numbers as in the prepared two-component samples were analyzed. All pigments were successfully identified in commercial products in the MeV-SIMS mass spectra through molecular and larger specific fragment ion peaks in the positive-ion mode. The main advantages of MeV-SIMS over other techniques used in SOPs identification, like pyrolysis gas chromatography mass spectrometry (Py-GC/MS), direct-temperature resolved mass spectrometry (DTMS), and laser desorption ionization mass spectrometry (LDIMS), can be summarized as follows: (i) pigments and binders can be detected simultaneously in the same mass spectrum acquired over a short measurement time (up to 500 s), (ii) only small sample flakes are required for the measurements, which are analyzed without any chemical treatment prior to the analyses, (iii) samples are not consumed during the analyses and can be reused for other measurements, e.g., multielemental analysis by other ion beam analysis (IBA) techniques, such as particle-induced X-ray emission (PIXE). Compared to, e.g., Raman spectroscopy, the significant benefit of MeV-SIMS is the exact identification of the SOPs in the paints even if pigments of similar structures are measured.

Introduction of a method to calculate cumulative age- and gender-specific lifetime attributable risk (LAR) of cancer in populations after a large-scale nuclear power plant accident.

The effect of age and gender in risk estimates related to long-term residence in areas contaminated by nuclear power plant fallout was evaluated by applying the lifetime attributable risk (LAR) concept to an existing exposure model that was previously used for cumulative effective dose estimates. In this study, we investigated the influence of age distribution on the number of cancer cases by applying five different age distributions from nuclear power-producing countries (India, Japan, South Korea, and the United States), and Egypt because of intentions to develop nuclear power. The model was also used to estimate the effective dose and gender-specific LAR as a function of time after fallout for the offspring of the population living in 137Cs fallout areas. The principal findings of this study are that the LAR of cancer incidence (excluding non-fatal skin cancers) over 70 y is about 4.5 times higher for newborn females (5.4% per MBq m-2 of initial 137Cs ground deposition) than the corresponding values for 30 y old women (1.2% per MBq m-2 137Cs deposition). The cumulative LAR for newborn males is more than 3 times higher (3.2% versus 1.0% per MBq m-2 137Cs deposition). The model predicts a generally higher LAR for women until 50 y of age, after which the gender difference converges. Furthermore, the detriment for newborns in the fallout areas initially decreases rapidly (about threefold during the first decade) and then decreases gradually with an approximate half-time of 10-12 y after the first decade. The age distribution of the exposed cohort has a decisive impact on the average risk estimates, and in our model, these are up to about 65% higher in countries with high birth rates compared to low birth rates. This trend implies larger average lifetime attributable risks in countries with a highly proportional younger population. In conclusion, the large dispersion (up to a factor of 4 between newborns and 30 y olds) in the lifetime detriment per unit ground deposition of 137Cs over gender and age in connection with accidental nuclear releases justifies the effort in developing risk models that account for the higher radiation sensitivity in younger populations.

Dynamics and Kinetics of Methanol-Graphite Interactions at Low Surface Coverage.

The processes of molecular clustering, condensation, nucleation, and growth of bulk materials on surfaces, represent a spectrum of vapor-surface interactions that are important to a range of physical phenomena. Here, we describe studies of the initial stages of methanol condensation on graphite, which is a simple model system where gas-surface interactions can be described in detail using combined experimental and theoretical methods. Experimental molecular beam methods and computational molecular dynamics simulations are used to investigate collision dynamics and surface accommodation of methanol molecules and clusters at temperatures from 160 K to 240 K. Both single molecules and methanol clusters efficiently trap on graphite, and even in rarified systems methanol-methanol interactions quickly become important. A kinetic model is developed to simulate the observed behavior, including the residence time of trapped molecules and the quantified Arrhenius kinetics. Trapped molecules are concluded to rapidly diffuse on the surface to find and/or form clusters already at surface coverages below 10-6 monolayers. Conversely, clusters that undergo surface collisions fragment and subsequently lose more loosely bound molecules. Thus, the surface mediates molecular collisions in a manner that minimizes the importance of initial cluster size, but highlights a strong sensitivity to surface diffusion and intermolecular interactions between the hydrogen bonded molecules.

Background reduction at DTU Nutech surface gamma laboratory.

Sources of background and background variation in a BEGe type HPGe detector located in a surface laboratory were identified. Different strategies for background reduction were applied. A cosmic veto was installed, and optimised using a digital acquisition system in list-mode with time-stamped data. This resulted in the reduction of total background by a factor of 1.4. Thermal and fast neutron fluxes were also calculated. The radon induced background component and its variation were significantly reduced.

A gas breathing hydrogen/air biofuel cell comprising a redox polymer/hydrogenase-based bioanode.

Hydrogen is one of the most promising alternatives for fossil fuels. However, the power output of hydrogen/oxygen fuel cells is often restricted by mass transport limitations of the substrate. Here, we present a dual-gas breathing H2/air biofuel cell that overcomes these limitations. The cell is equipped with a hydrogen-oxidizing redox polymer/hydrogenase gas-breathing bioanode and an oxygen-reducing bilirubin oxidase gas-breathing biocathode (operated in a direct electron transfer regime). The bioanode consists of a two layer system with a redox polymer-based adhesion layer and an active, redox polymer/hydrogenase top layer. The redox polymers protect the biocatalyst from high potentials and oxygen damage. The bioanodes show remarkable current densities of up to 8 mA cm-2. A maximum power density of 3.6 mW cm-2 at 0.7 V and an open circuit voltage of up to 1.13 V were achieved in biofuel cell tests, representing outstanding values for a device that is based on a redox polymer-based hydrogenase bioanode.

A fully protected hydrogenase/polymer-based bioanode for high-performance hydrogen/glucose biofuel cells.

Hydrogenases with Ni- and/or Fe-based active sites are highly active hydrogen oxidation catalysts with activities similar to those of noble metal catalysts. However, the activity is connected to a sensitivity towards high-potential deactivation and oxygen damage. Here we report a fully protected polymer multilayer/hydrogenase-based bioanode in which the sensitive hydrogen oxidation catalyst is protected from high-potential deactivation and from oxygen damage by using a polymer multilayer architecture. The active catalyst is embedded in a low-potential polymer (protection from high-potential deactivation) and covered with a polymer-supported bienzymatic oxygen removal system. In contrast to previously reported polymer-based protection systems, the proposed strategy fully decouples the hydrogenase reaction form the protection process. Incorporation of the bioanode into a hydrogen/glucose biofuel cell provides a benchmark open circuit voltage of 1.15 V and power densities of up to 530 µW cm-2 at 0.85 V.

The Open Circuit Voltage in Biofuel Cells: Nernstian Shift in Pseudocapacitive Electrodes.

In the development of biofuel cells great effort is dedicated to achieving outstanding figures of merit, such as high stability, maximum power output, and a large open circuit voltage. Biofuel cells with immobilized redox mediators, such as redox polymers with integrated enzymes, show experimentally a substantially higher open circuit voltage than the thermodynamically expected value. Although this phenomenon is widely reported in the literature, there is no comprehensive understanding of the potential shift, the high open circuit voltages have not been discussed in detail, and hence they are only accepted as an inherent property of the investigated systems. We demonstrate that this effect is the result of a Nernstian shift of the electrode potential when catalytic conversion takes place in the absence or at very low current flow. Experimental evidence confirms that the immobilization of redox centers on the electrode surface results in the assembled biofuel cell delivering a higher power output because of charge storage upon catalytic conversion. Our findings have direct implications for the design and evaluation of (bio)fuel cells with pseudocapacitive elements.

Characterisation of an ultra low-background point contact HPGe well-detector for an underground laboratory.

Since a few years there are well-type HPGe-detectors with a small, point-like, anode contacts available commercially. This paper describes the characterisation of the first ultra low-background, so-called, SAGe™ well detector with regards to resolution and background performance. Inside a passive lead/copper shield in the underground laboratory HADES a background count rate of 690 ± 6d-1 (268 ± 3d-1 per kg Ge) was recorded 19 months after taking it underground.

Digital gamma-gamma coincidence HPGe system for environmental analysis.

The performance of a new gamma-gamma coincidence spectrometer system for environmental samples analysis at the Center for Nuclear Technologies of the Technical University of Denmark (DTU) is reported. Nutech Coincidence Low Energy Germanium Sandwich (NUCLeGeS) system consists of two HPGe detectors in a surface laboratory with a digital acquisition system used to collect the data in time-stamped list mode with 10ns time resolution. The spectrometer is used in both anticoincidence and coincidence modes.

Water accommodation and desorption kinetics on ice.

The interaction of water vapor with ice remains incompletely understood despite its importance in environmental processes. A particular concern is the probability for water accommodation on the ice surface, for which results from earlier studies vary by more than 2 orders of magnitude. Here, we apply an environmental molecular beam method to directly determine water accommodation and desorption kinetics on ice. Short D2O gas pulses collide with H2O ice between 170 and 200 K, and a fraction of the adsorbed molecules desorbs within tens of milliseconds by first order kinetics. The bulk accommodation coefficient decreases nonlinearly with increasing temperature and reaches 0.41 ± 0.18 at 200 K. The kinetics are well described by a model wherein water molecules adsorb in a surface state from which they either desorb or become incorporated into the bulk ice structure. The weakly bound surface state affects water accommodation on the ice surface with important implications for atmospheric cloud processes.

Dynamics of the O + CN reaction and N + CO scattering on two coupled surfaces.

Spin-orbit coupling between the two collinear (2)Pi and (4)Sigma(-) potential energy surfaces for the NCO system are calculated using the RASSI method with CASSCF wave functions as basis set. The GDVR method has been used to interpolate a spin-orbit coupling surface. Wave packet and quasi-classical trajectory surface hopping calculations have been performed and compared for both the O((3)P) + CN(X(2)Sigma(+)) --> N((4)S) + CO(X(1)Sigma(+)) reaction and for electronically inelastic scattering in the N + CO channels. The O + CN nonadiabatic reaction probabilities are small. The wavepacket study gives a resonance structure. Also for the N + CO electronically inelastic scattering the wave packet calculations give a distinct resonance structure with peak transition probabilities up to around 10%, which is somewhat lower than the trajectory surface hopping results.

A new reaction path for the C + NO reaction: dynamics on the 4A'' potential-energy surface.

We present a new reaction path without significant barriers for the C + NO reaction, forming ground state N((4)S) and CO. Electronic structure (CASPT2) calculations have been performed for the two lowest (4)A'' states of the CNO system. The lowest of these states shows no significant barriers against reaction in the C + NO or O + CN channels. This surface has been fitted to an analytical function using a many-body expansion. Using this surface, and the previously published (2)A' and (2)A'' surfaces [Andersson et al., Phys. Chem. Chem. Phys., 2000, 2, 613; Andersson et al., Chem. Phys., 2000, 259, 99], we have performed quasiclassical trajectory (QCT) calculations, obtaining rate coefficients for the C((3)P) + NO(X(2)Pi) --> CO(X(1)Sigma(+)) + N((4)S,(2)D) and C((3)P) + NO(X(2)Pi) --> O((3)P) + CN(X(2)Sigma(+)) reactions. We have also simulated the crossed molecular beam experiments of Naulin et al. [Chem. Phys., 1991, 153, 519] The inclusion of the (4)A'' surface in the QCT calculations gives excellent agreement with experiments. This is the first time an adiabatic pathway from C((3)P) + NO(X(2)Pi) to CO(X(1)Sigma(+))+N((4)S) has been reported.

A linearized path integral description of the collision process between a water molecule and a graphite surface.

Quantum effects in the scattering and desorption process of a water molecule from a graphite surface are investigated using the linearized path integral model. The graphite surface is quantized rigorously using the fully quantum many-body Wigner transform of the surface Boltzmann operator, while the water molecule is treated as rigid. Classical dynamics with these quantized initial conditions show that quantizing the surface at 100 and 300 K results in markedly different results, compared to a fully classical analysis. The trapping probability (defined as the probability of multiple encounters with the surface) is not sensitive to the choice of dynamical treatment, but the residence time on the surface is much shorter in the quantum case. At 300 K the transiently trapped molecules desorb from the surface with a rate constant which is 60-70% larger than the corresponding classical value. Lowering the surface temperature to 100 K decreases the quantum rate constant by approximately a factor of 3 while all trapped molecules stick to the surface in the classical case. The stability of the quantum initial state for the highly anisotropic graphite crystal is discussed in detail as well as the dynamical consequences of energy redistribution during the scattering process. The graphite surface application demonstrates that the Boltzmann operator Wigner transform for a system with 900 degrees of freedom can be obtained by the so-called gradient implementation [Poulsen et al. J. Chem. Theory Comput. 2006, 2, 1482] of the underlying Feynman-Kleinert effective frequency theory, an implementation that only requires a force and potential routine for the system at hand, and hence is applicable to any molecule-surface collision problem.

Comparison of classical and quantum dynamics for collinear cluster scattering.

The collinear dynamics of a cluster of four particles colliding with a fixed particle representing a surface is investigated using a four-dimensional wave packet approach. The properties of the system are chosen to resemble a water cluster interacting with graphite, but a deeper surface-particle potential is also considered causing significant dissociation of the cluster. Having four different product arrangement channels the system is quantum mechanically demanding but still manageable. The dynamical richness makes it a suitable benchmark system for evaluation of classical and quantum/classical schemes. The average energy transferred to the cluster and the three dissociation probabilities are presented as function of the initial state of the cluster. In addition to wave packet data, results obtained using quasiclassical as well as Wigner sampled classical trajectories are presented. The main conclusion is that classical mechanics can describe the dynamics of the system in a very satisfactory way. Including zero-point energy in the classical simulations is particularly important for a good description of dissociation but less important for energy transfer.