Deciphering the influence of PdII and PdIV oxidation states on non-standard chemical bonds within bis(jN-heterocyclic carbene) complexes: insights from DFT.

Bis-N-heterocyclic carbene ligands (bis(NHC)) have introduced a new approach to designing homogeneous and heterogeneous catalysts, demonstrating the versatility of ligand concepts in catalysis. This study presents a computational analysis of palladium (+ii and +iv) complexes containing either a normally (bis(nNHC)) or an abnormally (bis(aNHC)) bound CH2-bridged bis-N-heterocyclic carbene ligand; in addition, ancillary ligands are permuted from chlorides (X = Cl) to bromides (X = Br). Density functional theory at the B3PW91/6-31G(d)/Lanl2DZ level in the gas phase was used to investigate the electronic structure and bonding properties of bis(NHC)PdIIX2 and bis(NHC)PdIVX4 for bis(NHC) palladium(ii) dihalide and palladium(iv) tetrachloride complexes, respectively. Results indicate that all of the palladium complex structures prefer a flexible boat-type conformation with an average C 2v symmetry, according to bond property (Ccarbene-Pd and Pd-Cl[Br]) analysis. The strength of these bonds depends on coordinating halide ions (Cl- and Br-), the type of ligand (bis(nNHC) and bis(aNHC)), and the palladium oxidation state (+ii and +iv). Analysis of thermodynamic parameters (ΔH 0, ΔG 0, and ΔE bind) shows an increase in values from an abnormal to normal chelating mode in tetrahalides, whereas the opposite is observed for dihalide complexes. The lower π-backbonding ability of the metal, which is influenced by the quantity and size of halide ions involved, could be one possible explanation for this deficiency.

Mononuclear half-sandwich nd7 metallo drug complexes based on bidentate N∩N dendritic scaffolds: DFT (B3LYP; BP86 and B3PW91) examination.

Through an use of three functionals (B3PW91, B3LYP and BP86) associated to a generic basis set LanL2DZ for transition metals (as well as halogen atoms) and 6-311+G (d,p) for others atoms, an examination of the bonding properties of a series of mononuclear half-sandwich nd7 transition metal (anticancer) complexes based on N∩N dendritic scaffolds (L) has been done. Collectively, complexes studied have adopted the piano-stool environment. An examination of the performance of each functional has shown that for the most reliable geometrical analysis of Metal-Nitrogen and Metal-Halogen bonds, the B3LYP and B3PW91 functionalities are suitable respectively. Regardless of the halogen ligand adopted, the B3LYP metal-nitrogen bond lengths are the most widely overestimated. A correlation has been built between the retained charge on each divalent transition metal cation and its metal ion affinity (MIA). Topological examinations reveal the higher instability of metal-N bonds compared to metal-X ones (X = Cl and Br). By the mean of the energy decomposition analysis, a predominant electrostatic character of metal … halogen and [LCP]- … [MX]+ interaction has been demonstrated. The transition metal atom … (hydrophobic) surface (Cp*) interaction is most pronounced for the chloride rhodium complexes of rhodium (combined with (E)-N-(pyridin-2-ylmethylene) Propan-1-amine and 2,2'- dipyridylketone ligands and iridium combined with 2,2'- dipyridylketone ligand. The charge decomposition analysis displays the weakening of the [Formula: see text] bonds in the studied complexes.

Low prevalence of relative age effects in Luxembourg's male and female youth football.

The relative age effect (RAE) is a well-established phenomenon in football. However, while the majority of previous studies focussed on established football nations, it remains unclear if the constraint of a limited population of soccer players in smaller countries associated with less strict selection procedures may reduce the risk of RAE. This study aims to investigate the RAE in Luxembourg that follows an 'open-door' selection policy in youth football due to the limited pool of players. Birthdates from all licensed and actively playing Luxembourgish youth footballers including all players of the youth national teams (396 girls and 10981 boys) competing in the season 2018/2019 were analysed and categorised into birth quarters and semesters. To further investigate a performance dependence of the RAE in amateur leagues, success was determined based on the teams' rankings at the end of the season. Differences between observed and expected birthdate distributions were calculated across all licensed players and age groups, within the national teams, and for the top- and bottom-tier football teams using chi-square statistics. While a RAE was absent across all age groups (except U7), significant RAEs with high effect sizes were observed in the top-level and national teams. These findings contrast the substantial RAE effects in large football nations and suggest that open selection systems might reflect an environmental constraint that limit the prevalence of RAE in football. Further, this study indicates that a performance dependence of the RAE is not limited to high level football but already occurs on an amateur level.

DFT/B3LYP and BP86 examination of mononuclear half-sandwich nd7 metallo drug complexes based on N∩O dendritic scaffolds.

In this paper, we have explored the bonding properties of a series of mononuclear half-sandwich nd7 anticancer complexes based on N∩O dendritic scaffolds (L) using two functionals (B3LYP and BP86) with generic basis set (LanL2DZ for transition metals (as well as halogen atoms) and 6-311 + G (d,p) for others atoms. The geometry optimization of structures have led to the adoption of the piano-stool environment and the formation of kings of intermolecular hydrogen bonding: CH … X (Cl,Br) (2.619-2.954) and CH...O (2.266-2.973 Å) interaction. The metal (M)-bromine bond distances have shown to be significantly higher than metal-chlorine ones. In chloride complexes, salicylaldimine ligand-Co2+ (-3097.15 kJ/mol) and salicylaldimine ligand-Ir2+ (-3436.78 kJ/mol) interactions are stronger. Except for cobalt complexes, the interaction energies are underestimated by B3LYP functional, by contrast B3LYP HOMO-LUMO gaps obtained are highly greater. The metal ion affinity (MIA) is increasing in the order: Ir+2

Tile Drainage as a Hydrologic Pathway for Phosphorus Export from an Agricultural Subwatershed.

Cyanobacteria growth in Missisquoi Bay of Lake Champlain is triggered by the P load carried by tributaries in surrounding watersheds where agriculture is a dominant land use. The objective of this study was to apportion the total P (TP) load in streamflow from an agricultural subwatershed into distinct hydrologic pathways: groundwater resurgence, surface runoff, and tile drainage components (matrix flow and preferential flow). Stream discharge during peak flow was separated into these four components using electrical conductivity (EC)-discharge relationships developed from the stream water EC at the subwatershed outlet and from EC values of surface runoff and tile drain water in 10 fields within the subwatershed. The four-component hydrograph model revealed that 46 to 67% of the TP load at the outlet originated from surface runoff during peak flow. Preferential flow was responsible for most of the particulate P and dissolved reactive P loads lost through tile drainage. Groundwater resurgence was a minor source of TP, whereas other sources such as streambank erosion and resuspended sediments contributed up to 21% of the TP load and from 36 to 41% of the particulate P load at the subwatershed outlet. This work confirms that tile drainage contributes to the TP load in agricultural subwatersheds in the Missisquoi Bay region.

Birdshot Retinochoroidopathy: Prognostic Factors of Long-term Visual Outcome.

PURPOSE: To determine the prognostic factors of long-term visual outcome in birdshot retinochoroidopathy (BRC). METHODS: Design: Retrospective case series. Study Population: Successive HLA-A29+ BRC patients whose latest visit was between May and August 2013 at a single tertiary center (Pitié-Salpétrière Hospital, Paris). OBSERVATION PROCEDURE: Endpoint visual status (remission or deterioration) was determined for each patient based on clinical and ancillary data from the latest visit including optical coherence tomography (OCT), automated visual field (AVF), and angiograms. Main Outcome Measure: Epidemiologic, clinical, OCT, AVF, angiographic, and electrophysiological data at baseline were correlated to final visual status. RESULTS: Fifty-five patients were included. Mean observation period was 8 years (range: 0.6-23 years). Mean disease duration was 9.8 years (range: 1.2-32.7 years). Female-to-male sex ratio was 1.6:1. Factors of good visual prognosis (remission vs deterioration) included at baseline: late age of disease onset (49.5 vs 45 years, P = .05), presence of vitreous inflammatory reactions >2+ (35.9% vs 6.2%, P = .04), vascular leakage on fluorescein angiograms (FA) (44.4% vs 12.5%, P = .03), absence of macular pigment epithelium atrophy on FA (88.9% vs 62.5%, P = .05), and presence of macular edema on OCT (33.3% vs 6.2%, P = .04). Preserved electrooculography light peak and Arden ratio (P = .06) and presence of choroidal spots on infracyanine green angiograms (80.0% vs 53.3%, P = .08) seemed associated with the best prognoses. CONCLUSION: This study suggests a series of prognostic factors of long-term visual outcome in BRC. Keeping in mind the insidious evolution of the disease, knowledge of such prognostic factors should help tailor the treatment and monitoring of birdshot patients.

Visual Acuity in Birdshot Retinochoroidopathy Evaluation.

PURPOSE: To determine the statistical correlation between visual acuity (VA) and various quantitative parameters relevant to birdshot retinochoroidopathy (BRC) evaluation. DESIGN: Hospital-based retrospective observational study. METHODS: setting: Institutional. STUDY POPULATION: Consecutive HLA29+ BRC patients were included between May and August 2013 at a single tertiary center (Pitié-Salpétrière Hospital, Paris). OBSERVATION PROCEDURES: Demographic data and quantitative parameters relevant to BRC at baseline were collected: VA, degree of anterior and posterior inflammatory reaction, foveal thickness measured by optical coherence tomography (OCT), Arden ratio, and electrooculography (EOG) light peak. MAIN OUTCOME MEASURES: Correlation between VA and the other parameters of the ipsilateral and fellow eye was performed using Spearman rank correlation coefficients. RESULTS: Fifty-five patients were included. Mean VA was 6/9.5 in the right eye (OD) and 6/12 in the left eye (OS). Mean foveal thickness was 240 µm OD (range: 112-606) and 251 µm OS (range: 85-662). Mean Arden ratio was 159% OD and 160% OS. EOG light peak was 714 mV OD (range: 316-1379) and 746 mV OS (range: 272-1652). VA of a given eye was moderately correlated with VA of the contralateral eye (r = 0.4). On the contrary, all other parameters showed a strong correlation between both eyes (all r > 0.7, P < .01). Overall, none of the studied parameters was correlated with its VA (all r < 0.5). CONCLUSION: In BRC, visual acuity alone does not seem to fully reflect the disease severity in terms of clinical or ancillary quantitative findings at baseline.

Ophthalmologic impairment during adulthood in central congenital hypoventilation syndrome: a longitudinal cohort analysis of nine patients.

BACKGROUND: Congenital central hypoventilation syndrome (CCHS) is a rare dysgenetic form of neurocristopathy associated with dysfunction of the autonomic nervous system. Ophthalmologic abnormalities are reported in CCHS children, and range from pupillary and iris abnormalities to ptosis, strabismus and convergence deficiency. Since earlier CCHS diagnosis and multidisciplinary management, combined with improved ventilatory support techniques, the lifespan of children with CCHS has been considerably lengthened. The oldest of them have now reached adult age and we report in this study the results of their ophthalmologic examination. MATERIALS AND METHODS: Nine CCHS adult patients were prospectively included during a 14-month period. Each patient underwent complete ophthalmologic examination, static pupillometry with scotopic and photopic pupillary diameter (PD) measures, Humphrey 24-2 visual field analysis, macular OCT and complete orthoptic assessment including a Hess-Lancaster test. RESULTS: Ophthalmologic abnormalities were found in six of the nine patients (66%). The main features were strabismus in six patients (66%). Four patients (44%) displayed abnormal pupillary function, with a decrease in average scotopic PD (3.8 ± 1.4 mm), average photopic PD (3.5 ± 1.2 mm), and average percentage of pupillary constriction (7.6 ± 8.5%). Three patients (33%) exhibited iris abnormalities such as iris atrophy, smooth iris surface and atrophic sphincter. CONCLUSION: This study allowed the description of ophthalmologic abnormalities occurring in CCHS in a series of adult patients, thus improving current knowledge of the disease. The prevalence of pupillary and iris lesions were lower than those observed in a series of children, suggesting that they could be considered as systemic disease severity markers.

Safety and feasibility of intra-arterial bivalirudin bolus administration during primary angioplasty.

AIM: We investigated the feasibility and safety of intra-arterial bivalirudin bolus during primary angioplasty. BACKGROUND: Bivalirudin has been shown to be an effective and safe anticoagulant during angioplasty. However, in the Harmonizing Outcomes with Revascularization and Stents in Acute Myocardial Infarction trial, the bivalirudin group experienced higher acute stent thrombosis rate compared with the heparin and glycoprotein IIb/IIIa inhibitor group. One possible explanation is suboptimal systemic administration. METHODS: To prevent this possibility and to potentially prevent acute stent thrombosis, we administered intra-arterial bivalirudin bolus during primary angioplasty in 100 consecutive patients. RESULTS: Our observational study suggests safety with no bleeding episode and no observed acute stent thrombosis. CONCLUSION: We conclude that intra-arterial bivalirudin bolus during primary angioplasty is safe and could ensure effective systemic delivery of bivalirudin.

Impact of pre-operative regular physical activity on balance control compensation after vestibular schwannoma surgery.

Vestibular compensation after unilateral vestibular deafferentation is modulated by certain individual characteristics, such as pre-operative visual neurosensory preference or vestibular pattern. Physical activity (PA) allows the implementation of new sensorimotor and behavioral strategies leading to an improvement of balance control. This study aimed to evaluate the effect of the level of PA before surgery on balance compensatory mechanisms in patients after vestibular schwannoma (VS) surgery. Thirty patients with VS, 15 considered as regularly physically active and 15 as sedentary participated in this study, including an evaluation of gaze control by videonystagmography and postural control by a sensory organization test. Patients considered as physically active before surgery presented the best pattern of postural compensation, with the classical decrease in postural performances at short term (i.e. eight days) and the increase in postural performances at middle and long terms (i.e. 90 and 180 days, respectively) after surgery. For the sedentary patients, the consequences of surgery were more difficult to manage at short term, even though this did not prevent the ability to compensate well later on. Pre-operative practice of PA promotes the neuroplasticity of neural networks involved in motor learning, which allows to benefit of physical therapy more rapidly and efficiently.

Long-term effects of vestibular compensation on balance control and sensory organisation after unilateral deafferentation due to vestibular schwannoma surgery.

The time-course of central adaptive mechanisms after vestibular schwannoma surgical removal allows, 3 months after surgery (middle term), a satisfactory recovery of balance control. However, the long-term evolution of postural control beyond the end of usual medical follow-up remains unknown. This longitudinal prospective study aimed to assess the long-term effects of vestibular compensation on balance control and sensory organisation in patients operated on for vestibular schwannoma. Thirty-six patients with vestibular schwannoma underwent vestibular and sensory organisation tests, shortly before and 3 months, 6 months and 1 year after surgery. Postural control performances improved 3 months after surgery compared with before surgery; they continued to improve at 6 and 12 months after surgery, especially in conditions highly soliciting vestibular information. In the long term, strategies based on sensorimotor and/or behavioural substitution seem to be reinforced and fine-tuned, particularly in complex postural situations, for which only vestibular information is reliable to control balance.

Mucoepidermoid carcinoma of salivary glands in the pediatric age group: 18 clinical cases, including 11 second malignant neoplasms.

BACKGROUND: Salivary gland tumors represent 1% of head and neck tumors, with only 5% of these occurring in patients younger than 20 years. Mucoepidermoid carcinoma (MEC) is one of the most frequent salivary gland cancers among adults and children. METHODS: This survey was conducted among 34 French pediatric oncology departments. From 1980 to 2000, 18 cases were reported. RESULTS: Treatment included surgery or radiotherapy, or both. The 5-year survival rate was 93.7%. Eleven patients had been previously treated by radiotherapy and/or chemotherapy for a first malignant tumor, specifically, lymphoid leukemia (n = 4), lymphoma (n = 3), brain tumor (n = 2), sarcoma (n = 1), and retinoblastoma (n = 1). CONCLUSIONS: MEC is very rare in the pediatric age group. Treatment involves surgical removal of the tumor plus radiotherapy, according to histologic staging. MEC has a good prognosis in young patients. The survival rate does not differ in the subgroup of patients with MEC as a secondary tumor.

Sensorimotor postural rearrangement after unilateral vestibular deafferentation in patients with acoustic neuroma.

Unilateral vestibular lesion, as acoustic neuroma and its surgical removal, leads to impaired balance control. After initial vertigo and postural instability corresponding to unilateral vestibular deafferentation, improvement in symptoms and global balance functions occurs by a process called vestibular compensation. In this respect, this prospective study aimed to assess the differential contribution of sensory inputs to the regulation of posture during the recovery process after acoustic neuroma removal. Twenty-seven patients with acoustic neuroma underwent vestibular and posturographic testings, shortly before and 8 days, 1 month and 3 months after surgical removal of the tumour. Immediately after vestibular deafferentation, vestibular function was asymmetrical, postural performances were altered, especially in eyes closed conditions and in sensory challenged situations. One month, and more particularly 3 months after surgery, restoration and even improvement of vestibular and balance performances occurred, associated with a lower number of falls, development of more appropriate sensorimotor strategies and better resolution of sensorial conflicts. Postural perturbations are related to erroneous vestibular afferences, leading to incoherence in information about head position and interference with somatosensory and visual pathways. The time-course implementation of central adaptive mechanisms, characterized by substitution by other sensory afferences and new behavioural strategies, leads to an improvement of balance performance.

Hybrid revascularization using percutaneous coronary intervention and robotically assisted minimally invasive direct coronary artery bypass surgery.

Hybrid revascularization (HR) combines staged percutaneous coronary intervention (PCI) on stenoses in the non-left anterior descending (LAD) territories with minimally invasive direct coronary artery bypass (MIDCAB) using the left internal thoracic artery (LITA) to the LAD. The LITA-to-LAD graft, which has a 5-year patency rate of 95%, is the major determinant of the long-term survival for patients. Thus, HR aims to perform full revascularization without compromising the survival advantage of the LITA-to-LAD graft, while preserving the minimally invasive advantages associated with the percutaneous treatment of symptomatic coronary stenoses. We investigated whether HR was a valid alternative to conventional coronary artery bypass graft surgery in patients with multivessel coronary artery disease. We also present our early experiences with HR using a combined approach of advanced PCI and robotically-assisted MIDCAB.