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The transfer of an oxygen atom from carbon dioxide (CO2) to a transition metal cation in the gas phase offers atomic level insights into single-atom catalysis for CO2activation. Given that these reactions often involve open-shell transition metals, they may proceed through intersystem crossing between different spin manifolds. However, a definitive understanding of such spin-forbidden reaction requires dynamical calculations on multiple global potential energy surfaces (PESs) coupled by spin–orbit couplings. In this work, we report global PESs and spin–orbit couplings for three low-lying spin (quintet, triplet, and singlet) states for the reaction between the niobium cation (Nb+) and CO2, which are used to investigate the nonadiabatic reaction dynamics and kinetics. Comparison with experimental data of kinetics and collision dynamics shows satisfactory agreement. This reaction is found to be very similar to that between Ta++ CO2. Specifically, our theoretical findings suggest that the rate-limiting step in this reaction is intersystem crossing, rather than potential barriers.

The aim of this consecutive, retrospective, nonrandomized study is to assess the safety and success of short-term heavy silicone oil removal after pars plana vitrectomy for complex retinal detachment. To date, the lengthening of the timing of silicone oil can lead to less visual gains and more complications is known.

Electrospun (e-spun) fibers are generally regarded as powerful tools for cell growth in tissue regeneration applications, and the possibility of imparting functional properties to these materials represents an increasingly pursued goal. We report herein the preparation of hybrid materials in which an e-spun d,l-polylactic acid matrix, to which chitosan or crystalline nanocellulose was added to improve hydrophilicity, was loaded with different amounts of silver(0) nanoparticles (AgNP) generated onto chestnut shell lignin (CSL) (AgNP@CSL). A solvent-free mechanochemical method was used for efficient (85% of the theoretical value by XRD analysis) Ag(0) production from the reduction of AgNO3by lignin. For comparison, e-spun fibers containing CSL alone were also prepared. SEM and TEM analyses confirmed the presence of AgNP@CSL (average size 30 nm) on the fibers. Different chemical assays indicated that the AgNP@CSL containing fibers exhibited marked antioxidant properties (EC50 1.6 ± 0.1 mg/mL, DPPH assay), although they were halved with respect to those of the CSL containing fibers, as expected because of the efficient silver ion reduction. All the fibers showed high cytocompatibility toward human mesenchymal stem cells (hMSCs) representative of the self-healing process, and their antibacterial properties were tested against the pathogens Escherichia coli(E. coli), Staphylococcus epidermidis, and Pseudomonas aeruginosa. Finally, competitive surface colonization as simulated by cocultures of hMSC and E. colishowed that AgNP@CSL loaded fibers offered the cells a targeted protection from infection, thus well balancing cytocompatibility and antibacterial properties.

The activation of carbon dioxide (CO2) by a transition-metal cation in the gas phase is a unique model system for understanding single-atom catalysis. The mechanism of such reactions is often attributed to a “two-state reactivity” model in which the high-energy barrier of a spin state correlating with ground-state reactants is avoided by intersystem crossing (ISC) to a different spin state with a lower barrier. However, such a “spin-forbidden” mechanism, along with the corresponding dynamics, has seldom been rigorously examined theoretically, due to the lack of global potential energy surfaces (PESs). In this work, we report full-dimensional PESs of the lowest-lying quintet, triplet, and singlet states of the TaCO2+system, machine-learned from first-principles data. These PESs and the corresponding spin–orbit couplings enable us to provide an extensive theoretical characterization of the dynamics and kinetics of the reaction between the tantalum cation (Ta+) and CO2, which have recently been investigated experimentally at high collision energies using crossed beams and velocity map imaging, as well as at thermal energies using a selected-ion flow tube apparatus. The multistate quasi-classical trajectory simulations with surface hopping reproduce most of the measured product translational and angular distributions, shedding valuable light on the nonadiabatic reaction dynamics. The calculated rate coefficients from 200 to 600 K are also in good agreement with the latest experimental measurements. More importantly, these calculations revealed that the reaction is controlled by intersystem crossing, rather than potential barriers.

The assessment of reading performance metrics is characterized by good values of intersession repeatability in patients with neovascular age-related macular degeneration with good best-corrected visual acuity. These findings are important if these measures be employed in trials assessing the visual outcome in patients with neovascular age-related macular degeneration.

Rate constants and product branching fractions were measured from 300–600 K for Fen–+ O2(n= 2–17) and for 300–500 K for FexNiy–+ O2(x+ y= 3–9) using a selected-ion flow tube (SIFT) apparatus. Rate constants for 46 species are reported. All rate constants increased with increasing temperature, and several were in excess of the Langevin–Gioumousis–Stevenson (LGS) capture rate at elevated temperatures. As with previously studied transition metal anion oxidation reactions, the collision limit is treated as the sum of the LGS limit along with a hard-sphere contribution, allowing for determination of activation energies. These values are compared to each other along with previous results for Nin–. Measured rate constants for all three series (Fen–, Nin–, and FexNy–) vary over a relatively narrow range (1–5 × 10–10cm3s–1at 300 K) being at least 15% of the collision rate constant. All reaction rate constants increase with temperature, described by small activation energies of 0.5–4 kJ mol–1. The data are consistent with an anticorrelation between the electron binding energy and rate constant, previously noted in other systems. The Fen–reaction produces a larger population of higher energy electrons than do the Nin–reactions, with FexNiy–producing an intermediate amount. The results suggest that the overall rate constant is limited by a small energetic barrier located at a large internuclear distance where electrostatic forces dominate, causing the potentials to be similar across systems, while the product formation is determined by the shorter-range, valence portion of the potential, which varies widely between systems.

Background: Kidney transplant recipients (KTRs) rely on immunosuppressants like mycophenolate to prevent organ rejection. However, mycophenolate often causes intestinal symptoms and inflammation in various organs, including the skin and the colon. While KTRs have an increased risk for skin cancer, the risk of colorectal cancer is not increased. Methods: Whole slide images from gut biopsies (Non-transplanted subjects n= 35, KTRs n= 49) were analyzed using the ImageJ and R programming environment. A total of 22,035 epithelial cells, 38,870 interstitial cells, 3465 epithelial cell mitoses, and 7477 endothelial cells, each characterized by multiple microscopy parameters, from a total of 1788 glands were analyzed. The large database was subsequently analyzed to verify the changes of inflammatory milieu in KTRs and in cancer. Results: KTRs without colon-cancer showed a significantly higher density of interstitial cells in the colon compared to non-transplanted patients. Moreover, the increase in interstitial cell number was accompanied by subtle modifications in the architecture of the colon glands, without altering the epithelial cell density. We could not identify significant structural modifications in cancer samples between KTRs and non-transplanted patients. Conclusions: Our findings demonstrate an increased number of resident interstitial cells in the colon of KTRs, as in other patients treated with mycophenolate. These changes are associated with subtle alterations in the architecture of colon glands. Graphical abstract:

Background Anterior Chamber bleeding without vitreous hemorrhage had been described after the removal of 23G vitrectomy cannulas. We report the case of an anterior chamber bleeding after an intravitreal Dexamethasone implant.Case Report One patient with macular edema due to central retinal vein occlusion in a vitrectomized eye underwent an intravitreal Dexamethasone implant. After the injection the patient suffered from anterior chamber bleeding without signs of vitreous hemorrhage. The complication resolved with a conservative treatment.Conclusion Anterior Chamber bleeding is a possible complication of dexamethasone implant, that can be treated in a conservative way.

Objective:: To serially assess fetal cardiac dimensions in congenital diaphragmatic hernia (CDH) and their relation to disease severity. Study design:: Retrospective analysis of CDH cases and matched controls. Mitral (MVd) and tricuspid (TVd) valve diameters, left (LV) and right (RV) ventricular length and area, Z-scores, were serially assessed at 24–26, 30–32, and 35–37 weeks gestational age (GA). Results:: In CDH cases MVd, MVd Z-score, and LV area were significantly reduced at 24–26 and 35–37 weeks GA. TVd, TVd Z-score, and RV area were significantly reduced at 24–26 weeks. RV area Z-score increased with advancing GA. MVd and MVd Z-score were significantly lower at 24–26 weeks GA in CDH who had a combined outcome of death and/or ECMO. Conclusions:: LV hypoplasia in CDH is characterized by reduced MVd from 24 weeks GA. MVd, and the ratio of mitral and tricuspid valve diameters at later gestations, may be potential predictors of disease severity.

Purpose To evaluate short-term peripapillary structural and vascular changes in DME after treatment with dexamethasone implant (DEX-I) and anti-VEGFs using OCT-A.Methods Sixty-five patients with naïve center-involving DME were enrolled. 33 of sixty five patients (group 1) underwent with single DEX-I 0.7 mg (Ozurdex, Allergan, Inc., USA), 32 of sixty-five (group 2) underwent with intravitreal injection of aflibercept 0.5 mg (Eylea, Bayer, Genentech, San Francisco, USA). The OCT acquisition was completed at the following visits: (i) “T1 visit” corresponding to the intravitreal injection of DEX-I or aflibercept in patients with naïve center-involving DME (ii) “T2 visit” corresponding to the examination performed 2 weeks after intravitreal injection of aflibercept and 1 month after DEX-I. The parameters analyzed were: (i) RPC vasculature density (VD); (ii) peripapillary retinal nerve fiber layer (pRNFL) thickness, and (iii) intraocular pressure (IOP).Results The RPC analysis showed a VD increase at T2 in both groups, although values did not reach statistical significance (48.12± 4.17 and 49.04 ± 4.23; P = 0.081 in Group 1 and 46.93± 3.16 and 47.17 ± 3.70; P = 0.087 in Group 2). Likewise, the pRNFL thickness and IOP fluctuations did not show statistically significant changes in in both groups among the different study visits.Conclusions After intravitreal injection (anti-VEGF or DEX-I), no significant short-term changes were found in peripapillary microvasculature, IOP and pRNFL thickness in diabetic eyes treated with anti-VEGF or DEX-I.

Thymic epithelial tumors (TETs) are rare malignancies associated with dysregulation of the immune system and humoral- and cell-mediated immunity abnormalities. Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) mRNA vaccine is effective in preventing coronavirus disease 2019 morbidity and mortality. The aim of this study was to evaluate the seroconversion in patients with TET after two doses of mRNA vaccine.

Rate constants and product branching fractions were measured for reactions of Ar+, O2+, and NO+with isoprene (2-methyl-1,3-butadiene C5H8) as a function of temperature. The rate constants are large (∼2 × 10–9cm3s–1) and increase with temperature, exceeding the ion-dipole/induced dipole capture rate. Adding a hard sphere term to the collision rate provides a more useful upper limit and predicts the positive temperature dependences. Previous kinetic energy-dependent rate constants show a similar trend. NO+reacts only by non-dissociative charge transfer. The more energetic O2+reaction has products formed through both non-dissociative and dissociative charge transfer, or possibly through an H atom transfer. The very energetic Ar+has essentially only dissociative products; assumption of statistical behavior in the dissociation reasonably reproduces the product branching fractions.

The room-temperature rate constants and product branching fractions of CaOn+(n= 0–3) + O3are measured using a selected ion flow tube apparatus. Ca++ O3produces CaO++ O2with k= 9 ± 4 × 10–10cm3s–1, within uncertainty equal to the Langevin capture rate constant. This value is significantly larger than several literature values. Most likely, those values were underestimated due to the reformation of Ca+from the sequential chemistry of higher calcium oxide cations with O3, as explored here. A rate constant of 8 ± 3 × 10–10cm3s–1is recommended. Both CaO+and CaO2+react near the capture rate constant with ozone. The CaO+reaction yields both CaO2++ O2(0.80 ± 0.15 branching) and Ca++ 2O2. Similarly, the CaO2+reaction yields both CaO3++ O2(0.85 ± 0.15 branching) and CaO++ 2O2. CaO3++ O3yield CaO2++ 2O2at 2 ± 1 × 10–11cm3s–1, about 2% of the capture rate constant. The results are supported using density functional calculations and statistical modeling. In general, CaOn++ O3yield CaOn+1++ O2, the expected oxidation. Some fraction of CaOn+1+is produced with sufficient internal energy to further dissociate to CaOn–1++ O2, yielding the same products as the oxidation of O3by CaOn+. Mesospheric Ca and Ca+concentrations are modeled as functions of day, latitude, and altitude using the Whole Atmosphere Community Climate Model (WACCM); incorporating the updated rate constants improves agreement with concentrations derived from lidar measurements.

Nonaqueous Li–O2batteries have the potential to aid in the electrification of our society due to their relatively high theoretical energy density. Unfortunately, the technology suffers from large degrees of irreversibility due to the aggressive chemical environment associated with the oxidation of the discharge product lithium peroxide. Herein, we present a study of a range of linear and cyclic amides and ureas as aprotic electrolyte solvents for the Li–O2battery, some of which show slight increases in reversibility relative to the well-established pseudo-stable glymes, although we find that none provide reversibility necessary to enable a rechargeable system. Using quantitative differential electrochemical mass spectrometry, acid titrations, and isotopic labeling of O2and carbon in the positive electrode, we provide insight into the degradation pathways for these solvents. In the companion article, we compare our experimental results presented here to solvent decomposition pathways including a Baeyer–Villiger oxidation mechanism.

The kinetics of Zr++ CH4are measured using a selected-ion flow tube apparatus over the temperature range 300–600 K and the pressure range 0.25–0.60 Torr. Measured rate constants are small, never exceeding 5% of the Langevin capture value. Both collisionally stabilized ZrCH4+and bimolecular ZrCH2+products are observed. A stochastic statistical modeling of the calculated reaction coordinate is used to fit the experimental results. The modeling indicates that an intersystem crossing from the entrance well, necessary for the bimolecular product to be formed, occurs faster than competing isomerization and dissociation processes. That sets an upper limit on the lifetime of the entrance complex to crossing of 10–11s. The endothermicity of the bimolecular reaction is derived to be 0.09 ± 0.05 eV, in agreement with a literature value. The observed ZrCH4+association product is determined to be primarily HZrCH3+not Zr+(CH4), indicating that bond activation has occurred at thermal energies. The energy of HZrCH3+relative to separated reactants is determined to be −0.80 ± 0.25 eV. Inspection of the statistical modeling results under best-fit conditions reveals reaction dependences on impact parameter, translation energy, internal energy, and angular momentum. Reaction outcomes are heavily affected by angular momentum conservation. Additionally, product energy distributions are predicted.

Background The role of video-assisted thoracoscopic segmentectomy in the treatment of clinical IA non-small-cell lung cancer is not well established. The aim of our retrospective analysis was to evaluate the oncological results of complex and simple video-assisted thoracoscopic segmentectomy.Methods From 2015 to June 2020, data of n = 163 consecutive patients undergoing video-assisted thoracoscopic segmentectomy for solitary pulmonary nodule were analysed. The Kaplan–Meier method, log-rank test and Cox regression were used to estimate, compare survivals and identify risk factors of worse oncological outcomes.Results In this period, n = 123 patients underwent video-assisted thoracoscopic segmentectomy for non-small-cell lung cancer: we performed n = 65 simple and n = 58 complex video-assisted thoracoscopic segmentectomy; n = 99 (80.5%) had a solid appearance on computed tomography scan and n = 78 (63.4%) a moderate-to-high [18F]-2-fluoro-2-deoxy-D-glucose (FDG)-positron emission tomographic computed tomography scan avidity. Mortality was 0%, and complications occurred in n = 14 (21.5%) and 9 (15.5%) patients. The median follow-up was 24 (range: 6−60) months and the 5-year overall survival was 96% without difference between video-assisted thoracoscopic segmentectomies (p= 0.16). Local recurrence developed in n = 2 (3.1%) and n = 3 (5.2%) patients; regional in n = 2 (3.1%) and 1 (1.8%) and distant in 8 (12.3%) and 2 (3.4%), without difference between video-assisted thoracoscopic segmentectomies (p= 0.51). The overall 5-year disease-free survival rate was 78%. Pathological upstaging was observed in n = 13 patients (nodal in n = 6, tumour in n = 7) and it was the only significant factor for worse disease-free survival at the multivariable analysis (hazard ratio: 2.43, 95% CI: 1.04−8.68, p= 0.049), value confirmed also in the group of intended video-assisted thoracoscopic segmentectomy (p= 0.047).Conclusions Pathological upstaging after simple or complex video-assisted thoracoscopic segmentectomy is a risk factor for recurrence and then video-assisted thoracoscopic segmentectomy should be considered an appropriate therapeutic option for selected stage IA non-small-cell lung cancer patients.

PurposeTo explore the potential relationships between macular vascular network and different adaptive optics (AO) metrics in patients with type 1 diabetes mellitus (DM1) with no signs (NoDR) or mild non-proliferative diabetic retinopathy (NPDR).DesignObservational cross-sectional study.MethodsForty eyes of consecutive patients with DM1 (12 NoDR and 28 NPDR) and 10 healthy age-matched control subjects were included. All patients and controls were imaged using AO retinal camera and PLEX Elite 9000 optical coherence tomography (OCT) angiography (OCTA). The AO outcome measures to evaluate the cone photoreceptor mosaic characteristics were as follows: (1) Cone density (CD); (2) Linear Dispersion Index (LDi) and (3) Heterogeneity Packing Index (HPi). The OCTA outcome measures included: (1) superficial capillary plexus (SCP) perfusion density (PD); (2) deep capillary plexus (DCP) PD and (3) the choriocapillaris (CC) flow deficit percentage (FD%).ResultsNPDR group exhibited a close relationship between cone metrics and CC FD. Notably, CC FD% increase along with LDi (p=0.035), while the increasing CC FD% were associated with reducing CD (p=0.042) and the HPi (p=0.017). Furthermore, the OCTA parameters, including PD SCP and DCP, showed a significant negative correlation with CD.ConclusionsOur results demonstrated the relationship between macular perfusion at both retinal and choroidal levels and the cone mosaic in patients with DM1 interpolating swept-source-OCTA and AO metrics. In NPDR eyes, the photoreceptor damage was accompanied by CC insufficiency since the early stages of the disease.

Calibration of satellite observations is crucial for ensuring the quality of retrieved products essential for meteorological and climate applications. Calibration is obtained and monitored through a cascade of stages, including postlaunch vicarious calibration/validation activities through comparison with independent reference measurements. Here, the vicarious calibration method using radiative transfer simulations based on reference radiosondes is considered in the framework of the calibration/validation activities for the Microwave Imager (MWI) and the Ice Cloud Imager (ICI) to be launched with the Second Generation of the EUMETSAT Polar System. This paper presents an overview of the uncertainty characterizing the vicarious calibration of MWI and ICI using radiosondes as performed within the EUMETSAT-funded VICIRS study. The uncertainty characterization is pursued following a metrological approach, providing a preliminary estimation of all the identified sources. The same approach is used to develop a rigorous method for estimating the number of comparison pairs (i.e., observations vs. simulations) needed to reach a certain level of accuracy in bias determination.

The reactivities of three perfluoroalkyl carboxylic acids (PFCAs) (perfluoropropanoic acid (C2F5COOH, PFPA), perfluorobutanoic acid (C3F7COOH, PFBA), and perfluorooctanoic acid (C7F15COOH, PFOA)) in a thermal, weakly ionized, argon/electron plasma were investigated from 300 to 600 K using a Langmuir probe–flowing afterglow apparatus. The results are supported by density functional theory calculations of the energetics of PFCA, CnF2n+1COOH, from n= 1 to 7. PFPA and PFBA attach electrons at a substantial fraction of the calculated capture rate; PFOA likely attaches electrons with similarly high efficiency, but the low vapor pressure of PFOA resulted in only qualitative results. All three compounds attach electrons dissociatively via HF elimination. The “acidity channel” (i.e., formation of H + CnF2n+1COO–), calculated to be slightly endothermic, is never observed even at higher temperatures where this channel would be energetically allowed. Attachment to perfluorooctanesulfonic acid (n-C8F17SO3H) is rapid, yielding the conjugate base n-C8F17SO3–as proton transfer to the electron is exothermic. At temperatures near 450 K (PFOA), 550 K (PFBA), or 600 K (PFPA), the parent neutrals thermally decompose as evidenced by abrupt changes in rate constants and branching ratios. PFPA and PFBA react with Ar+close to the calculated capture rate, and PFOA likely does as well. The reaction mechanism starts via charge transfer, which can then lead to a range of product ions. Reactions with Ar+yield fluorocarbon radicals, clarifying and supporting a previously proposed mechanism of PFCA degradation in an argon plasma.

We report kinetics studies of H3O+(H2O)n=0–3with isoprene (2-methyl-1,3-butadiene, C5H8) as a function of temperature (300–500 K) measured using a flowing afterglow-selected ion flow tube. Results are supported by density functional (DFT) calculations at the B3LYP/def2-TZVP level. H3O+(n= 0) reacts with isoprene near the collision limit exclusively via proton transfer to form C5H9+. The first hydrate (n= 1) also reacts at the collision limit and only the proton transfer product is observed, although hydrated protonated isoprene may have been produced and dissociated thermally. Addition of a second water (n= 2) lowers the rate constant by about a factor of 10. The proton transfer of H3O+(H2O)2to isoprene is endothermic, but transfer of the water ligands lowers the thermicity and the likely process occurring is H3O+(H2O)2+ C5H8→ C5H9+(H2O)2+ H2O, followed by thermal dissociation of C5H9+(H2O)2. Statistical modeling indicates the amount of reactivity is consistent with the process being slightly endothermic, as is indicated by the DFT calculations. This reactivity was obscured in past experiments due to the presence of water in the reaction zone. The third hydrate is observed not to react and helps explain the past results for n= 2, as n= 2 and 3 were in equilibrium in that flow tube experiment. Very little dependence on temperature was found for the three species that did react. Finally, the C5H9+proton transfer product further reacted with isoprene to produce mainly C6H9+along with a small amount of clustering.

Purpose: To report potential choroidal changes in eyes undergoing femtosecond laser cataract surgery (FLACS) and phacoemulsification surgery (PCS) by OCT.Methods: The patients were images by means Spectral Domain OCT imaging with EDI technology which may obtain OCT image. We exported a single EDI-OCT scan passing through the fovea and then it was imported into ImageJ program to perform a quantitative analysis.Main outcome measures: The main outcome measures were: (i) sub foveal choroidal thickness (SFCT); (ii) the choroidal vascularity index (CVI); and (iii) central retinal thickness (CRT).Results: At postoperative 1 week, FLACS group showed an increased CRT (241.2 ± 31.6–245.5 ± 36.4 µm; p= 0.016). Likewise, CVI and SFCT exhibited a slight increase but no statistically differences were highlighted (p> 0.05). At the follow-up visit of 1 month, all OCT parameters did not display any significant difference (p> 0.05). At post-operative 1 week, the PCS group displayed a significant increase in CRT, SFCT, and CVI. On the contrary, at the follow-up visit of 1-month, all choroidal parameters were characterized by a no statistically significant reduction (p> 0.05).Conclusions: Our study exhibited a significant increase in CT and CVI in eyes that underwent conventional cataract surgery. Femtosecond laser-assisted cataract extraction did not result in macular change due to less postoperative inflammation.

Extensive macular atrophy with pseudodrusen is preceded by subretinal deposits that progressively disappear with accumulation of subretinal pigment epithelium midreflective material creating an RPE–basal lamina–Bruch membrane separation with a discernible Bruch membrane. These changes may represent thick basal laminar deposits preluding the atrophic changes.

The direct formation of N-heterocycles from aromatic hydrocarbons has been observed in nitrogen-based low-temperature plasmas; the mechanism of this unusual nitrogen-fixation reaction is the topic of this paper. We used homologous aromatic compounds to study their reaction with reactive nitrogen species (RNS) in a dielectric barrier discharge ionization (DBDI) source. Toluene (C7H8) served as a model compound to study the reaction in detail, which leads to the formation of two major products at “high” plasma voltage: a nitrogen-replacement product yielding protonated methylpyridine (C6H8N+) and a protonated nitrogen-addition (C7H8N+) product. We complemented those studies by a series of experiments probing the potential mechanism. Using a series of selected-ion flow tube experiments, we found that N+, N2+, and N4+react with toluene to form a small abundance of the N-addition product, while N(4S) reacted with toluene cations to form a fragment ion. We created a model for the RNS in the plasma using variable electron and neutral density attachment mass spectrometry in a flowing afterglow Langmuir probe apparatus. These experiments suggested that excited-state nitrogen atoms could be responsible for the N-replacement product. Density functional theory calculations confirmed that the reaction of excited-state nitrogen N(2P) and N(2D) with toluene ions can directly form protonated methylpyridine, ejecting a carbon atom from the aromatic ring. N(2P) is responsible for this reaction in our DBDI source as it has a sufficient lifetime in the plasma and was detected by optical emission spectroscopy measurements, showing an increasing intensity of N(2P) with increasing voltage.

A selected-ion flow tube apparatus has been used to measure rate constants and product branching fractions of 2Ti+reacting with O2, CO2, and N2O over the range of 200–600 K. Ti++ O2proceeds at near the Langevin capture rate constant of 6–7 × 10–10cm3s–1at all temperatures to yield 4TiO++ O. Reactions initiated on doublet or quartet surfaces are formally spin-allowed; however, the 50% of reactions initiated on sextet surfaces must undergo an intersystem crossing (ISC). Statistical theory is used to calculate the energy and angular momentum dependences of the specific rate constants for the competing isomerization and dissociation channels. This acts as an internal clock on the lifetime to ISC, setting an upper limit on the order of τISC< 1e–11s. 2Ti++ CO2produces 4TiO++ CO less efficiently, with a rate constant fit as 5.5 ± 1.3 × 10–11(T/300)−1.1 ± 0.2cm3s–1. The reaction is formally spin-prohibited, and statistical modeling shows that ISC, not a submerged transition state, is rate-limiting, occurring with a lifetime on the order of 10–7s. Ti++ N2O proceeds at near the capture rate constant. In this case, both Ti+ON2and Ti+N2O entrance channel complexes are formed and can interconvert over a barrier. The main product is >90% TiO++ N2, and the remainder is TiN++ NO. Both channels need to undergo ISC to form ground-state products but TiO+can be formed in an excited state exothermically. Therefore, kinetic information is obtained only for the TiN+channel, where ISC occurs with a lifetime on the order of 10–9s. Statistical modeling indicates that the dipole-preferred Ti+ON2complex is formed in ∼80% of collisions, and this value is reproduced using a capture model based on the generic ion–dipole + quadrupole long-range potential.

Purpose: To report variation of choroidal thickness (CT) and choroidal vascularity index (CVI) in subjects with drusen and subjects with reticular pseudodrusen (RPD) compared with healthy individuals using the Spectral-domain (SD)-Optical Coherence Tomography with enhanced depth imaging (EDI) system.Design: A prospective, observational, cross-sectional study.Subjects: Eighty-four participants.Methods: The patients were imaged using the Heidelberg Spectralis device (Heidelberg Engineering, Heidelberg, Germany) with EDI mode. EDI-OCT images were exported and then imported into image analysis ImageJ software (National Institutes of Health, Bethesda) and a semiautomated algorithm was used for subsequent quantitative analysis.Main outcome measures: This study evaluated two choroidal parameters: (i) choroidal thickness (CT); (ii) choroidal vascularity index (CVI).Results: CT analysis was performed in three different regions: (i) foveal region, (ii) parafoveal region; (iii) perifoveal region. All the analyzed regions were significantly decreased in RPD pattern, as compared with both the drusen group (p< .005) and healthy eyes (p< .005). CVI was significantly decreased in the RPD pattern, as compared with healthy eyes (p< 0.001). However, the drusenoid pattern did not have statistical significance in comparison with the control group suggesting the lower incidence of this pattern on choroidal vasculopathy.Conclusions: We report CT and CVI difference in RPD and drusen eyes. The RPD pattern seems to be a consequence of an alteration in the choroidal vascularity resulting in severe ischemia and excessive hypoxia inducing an increased risk of late AMD compared to the drusenoid pattern.

Background: To investigate choroidal vascularity index (CVI) changes after oral eplerenone treatment in chronic central serous chorioretinopathy (cCSC) using the Spectral-domain (SD)-Optical Coherence Tomography (OCT) with enhanced depth imaging (EDI) mode. Methods: Thirty-six eyes of 18 patients suffering from cCSC with monolateral foveal subretinal fluid (FSRF) successfully treated with oral eplerenone treatment and 18 age-matched healthy subjects were enroled in this retrospective study. EDI-OCT images obtained using Heidelberg Spectralis OCT device in patients with cCSC and FSRF (group 1); fellow eye (group 2) or healthy patients (healthy) were exported and then imported into image analysis ImageJ software for subsequent quantitative analysis. The main outcome measures were luminal area (LA) and CVI. Results: A higher value of CVI was detected in group 1 compared to healthy eyes (p= 0.006). LA and CVI significantly reduced during follow up in group 1 and group 2. LA at 120 days was significantly lower compared to all previous time points both in group 1 and group 2 (p&lt; 0.001). Median and [1st -3rd quartile] CVI values were 0.8 [0.7; 1.1] at baseline, 0.8 [0.7; 0.9] at 30 days; 0.7 [0.6; 0.9] at 60 and 90 days and 0.6 [0.5; 0.8] at 120 days in group 1 (p= 0.007) and 0.7 [0.6; 0.9] at baseline, 0.7 [0.7; 0.8] at 30 days; 0.7 [0.6; 0.7] at 60 and 90 days and 0.6 [0.6; 0.7] at 120 days in group 2 (p= 0.018). Conclusions: Choroidal vascularity index reduced in cCSC patients after oral eplerenone treatment during follow up both in eyes with SRF and fellow eyes thus demonstrating the effectiveness of mineral corticoid receptor antagonists in recovering choroidal morphology.

Background: Genetic testing of patients with inherited kidney diseases has emerged as a tool of clinical utility by improving the patients’ diagnosis, prognosis, surveillance and therapy. Methods: The present study applied a Next Generation Sequencing (NGS)-based panel, named NephroPlex, testing 115 genes causing renal diseases, to 119 individuals, including 107 probands and 12 relatives. Thirty-five (poly)cystic and 72 non (poly)cystic individuals were enrolled. The latter subgroup of patients included Bardet-Biedl syndrome (BBS) patients, as major components. Results: Disease-causing mutations were identified in 51.5 and 40% of polycystic and non-polycystic individuals, respectively. Autosomal dominant polycystic kidney disease (ADPKD) patients with truncating PKD1variants showed a trend towards a greater slope of the age-estimated glomerular filtration rate (eGFR) regression line than patients with (i) missense variants, (ii) any PKD2mutations and (iii) no detected mutations, according to previous findings. The analysis of BBS individuals showed a similar frequency of BBS4,9,10and 12mutations. Of note, all BBS4-mutated patients harbored the novel c.332+1G>GTT variant, which was absent in public databases, however, in our internal database, an additional heterozygote carrier was found. All BBS4-mutated individuals originated from the same geographical area encompassing the coastal provinces of Naples. Discussion: In conclusion, these findings indicate the potential for a genetic panel to provide useful information at both clinical and epidemiological levels. Graphic abstract:

An automatable CT protocol and technologist workflow metric allowing for the quantification of CT iodine contrast agent enhancement was developed and applied to 312 patients.

The kinetics of successive reactions of acetylene (C2H2) initiated on either vanadium or iron atomic cations have been investigated under thermal conditions using the variable-ion source and temperature-adjustable selected-ion flow tube apparatus. Consistent with the literature results, the reaction of Fe++ C2H2primarily yields Fe+(m/z= (C2H2)3); however, analysis via quantum chemical calculations and statistical modeling shows that the mechanism does not form benzene upon the third acetylene addition. The kinetics are more consistent with successive addition of three acetylene molecules, yielding Fe+(C2H2)3, followed by an addition of a fourth acetylene molecule, initiating cyclotrimerization, yielding either Fe+(C2H2) + neutral benzene or Fe+(Bz) + acetylene, where Bz is a benzene ligand. In contrast, the reaction of V++ C2H2yields products via successive associations V+(m/z= (C2H2)n) either with or without a bimolecular step involving loss of one H2and V+C2(m/z= (C2H2)m), where nand mextend at least up to 11 under conditions of 0.32 Torr at 300 K. Stabilized V+(Bz) is not a significant intermediate in the association mechanism. We propose a plausible mechanism for the generation of neutral benzene in this reaction and compare with the Fe+results. The reaction steps that produce benzene result in turnover of the single-atom catalyst, and the large hydrocarbons produced that remain associated to the catalyst are proposed to be polycyclic aromatic hydrocarbons.

This pilot study examined an 8‐week yoga‐mindfulness intervention with girls in the juvenile justice system. Pre‐ and posttest data were collected via the Mindful Awareness and Attention Scale for Adolescents (MAAS‐A). Paired ttests demonstrated a significant increase in mean MAAS‐A scores.

We describe our initial experience with the admission of 129 patients for 132 episodes of ventilator-dependence to a self-contained ventilator-dependent unit (VDU) in a general hospital and present a survival [...]

Historically, anaerobic bacteria as monomicrobial pathogens or components of polymicrobial infections have been found to play a minor role in osteomyelitis. Various Actinomycesspecies reside as constituents of the normal human microbial flora found in the oropharynx and in the most people may also be present as commensal microorganisms in the gastrointestinal, genitourinary, and, to a lesser degree, the upper respiratory tracts. Bone infections due to Actinomycesspecies are relatively uncommon and usually associated with concomitant cervicofacial disease. To date, only a sparse amount of cases of long bone osteomyelitis due to Actinomycesbacteria have been published in the medical literature. We report a case of monomicrobial subacute late-onset tibia bone osteomyelitis involving Actinomycespresenting 10 years after an open reduction and internal fixation surgical procedure performed to stabilize a traumatic fracture and review actinomycotic osteomyelitis including the rare association of Actinomyces odontolyticuswith long bone infections.

The balance of processes affecting electron density drives the dynamics of upper‐atmospheric electrical events, such as sprites. We examine the detachment of electrons from negatively charged atomic oxygen (O−) via collisions with neutral molecular nitrogen (N2) leading to the formation of nitrous oxide (N2O). Past research posited that this process, even without significant vibrational excitation of N2, strongly impacts the dynamics of sprites. We introduce updated rate coefficients derived from recent experimental measurements which suggest a negligible influence of this reaction on sprite dynamics. Given that previous rates were incompatible with the observed decay of the light emissions from sprite glows, our findings support that glows actually result from electron depletion in sprite columns. Sprites are transient, filamentary luminous structures appearing between approximately 50 and 85 km above Earth's surface. While the primary sprite activity is ephemeral, lasting mere thousandths of a second, certain luminous features persist up to a hundred times longer. The key to understanding these enduring structures lies in the evolution of free electron populations that facilitate electrical conductivity. Here we show that a process that influences this population is slower than previously thought. This may explain why luminous structures can persist for so long. Associative detachment of electrons in sprites proceeds almost exclusively from vibrationally excited N2We provide updated rate coefficients for electron associative detachmentIn models with the updated rates, sprite glows persist tens of milliseconds, in agreement with observations Associative detachment of electrons in sprites proceeds almost exclusively from vibrationally excited N2 We provide updated rate coefficients for electron associative detachment In models with the updated rates, sprite glows persist tens of milliseconds, in agreement with observations

Onco-nephrology is an emerging field in medicine. Patients with cancer may suffer from kidney diseases because of the cancer itself and cancer-related therapy. It is critical for nephrologists to be knowledgeable of cancer biology and therapy in order to be fully integrated in the multidisciplinary team and optimally manage patients with cancer and kidney diseases. In a recent international meeting, the key issues in this challenging clinical interface were addressed, including many unresolved basic science questions, such as the high tumor incidence in kidney transplant recipients. To this end, 70 highly qualified faculty members were gathered from all over the world to discuss these issues in 8 plenary sessions, including 5 keynote lectures. In addition, 48 young nephrologists and oncologists were invited to present their original observations that were highlighted in 2 large poster sessions.

We show how the powerful combination of temperature-dependent kinetics coupled with detailed statistical modeling can be used to derive dynamical information about transition state barrier heights, the importance of multiple entrance channel complexes, crossings between spin surfaces, energetics, product states, and other information for metal-ion reactions. The methods are not new, but with improved computers, ion sources, ion transport, and better detection techniques, the ability to derive such parameters from the combination of methods has improved greatly. Temperature-dependent kinetics is very sensitive to the above list of parameters because the energy is varied in a controlled way that can be easily modeled. The present measurements, performed in our variable-ion source temperature-adjustable selected-ion flow tube (VISTA-SIFT), have been enabled by advances in ion transport and injection improvements so that dim sources can be used. Replacing the quadrupole mass spectrometer detector with a time-of-flight mass spectrometer solved additional problems. Quantum chemical calculations have improved greatly and provide details about the surfaces, as well as frequencies, to use as starting points for the statistical modeling. For ion–molecule reactions, incorporation of both energy and angular momentum effects are important and we have developed an in-house computer program, based on the work of Juergen Troe, to rapidly compare statistical modeling predictions to the experimental data. As we show, modeling the kinetics data can often determine the most important parameters controlling the reactivity and deriving them is much simpler and usually more accurate than detailed ab initio calculations or dynamical modeling. Additionally, we show that even without statistical modeling, temperature-dependent rate constants as a function of metal anion cluster size can be used to show that such species react by the same mechanism as surfaces. In this review, we discuss reactions of metallic atomic ions, small metal oxide ions, mixed metal oxide ions, and a series of metallic anionic cluster reactions with small molecules such as CO, O2, CO2, N2O, CH4, and several other species. Particular attention was paid to reactions involving bond activation pertinent to catalysis.