Aim: To analyze the impact of intraoperative neurophysiological monitoring (IONM) on the extent of removal and long-term neurological outcomes in a series of grade II ependymomas.
Material And Methods: We retrospectively reviewed 88 consecutive patients who underwent surgical resection of an intramedullary spinal cord tumor (IMSCT) at the Clinic of Neurosurgery of the Clinical Center of Serbia in Belgrade between January 2012 and December 2017. In all, 39 patients (25 males and 14 females; mean age 46.
We have been puzzled by the involvement of weak organic and inorganic bases in the synthesis of metal-N-heterocyclic carbene (NHC) complexes. Such bases are insufficiently strong to permit the presumed required deprotonation of the azolium salt (the carbene precursor) prior to metal binding. Experimental and computational studies provide support for a base-assisted concerted process that does not require free NHC formation.
View Article and Find Full Text PDFA new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers.
View Article and Find Full Text PDFBacterial polyhydroxyalkanoates (PHAs) are a unique class of biodegradable polymers because of their biodegradability in ambient environments and structural diversity enabled by side-chain groups. However, the biosynthesis of PHAs is slow and expensive, limiting their broader applications as commodity plastics. To overcome such limitation, the catalyzed chemical synthesis of bacterial PHAs has been developed, using the metal-catalyzed stereoselective ring-opening (co)polymerization of racemic cyclic diolides (rac-8DL , R=alkyl group).
View Article and Find Full Text PDFOxygen evolution reaction (OER) catalysts that function efficiently in pH-neutral electrolyte are of interest for biohybrid fuel and chemical production. The low concentration of reactant in neutral electrolyte mandates that OER catalysts provide both the water adsorption and dissociation steps. Here it is shown, using density functional theory simulations, that the addition of hydrated metal cations into a Ni-Fe framework contributes water adsorption functionality proximate to the active sites.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2020
The limited potassium-ion intercalation capacity of graphite hampers development of potassium-ion batteries (PIB). Edge-nitrogen doping is an effective approach to enhance K-ion storage in carbonaceous materials. One shortcoming is the lack of precise control over producing the edge-nitrogen configuration.
View Article and Find Full Text PDFBackground: The sellar barrier concept reflects the association between the components of the roof of the pituitary fossa and the risk of intraoperative cerebrospinal fluid (CSF) leak in the surgery of pituitary adenomas. We based our concept in previous reports on the microsurgical anatomy of the pituitary fossa's superior wall. However, proof of the usefulness of this concept in endoscopic approaches is yet missing.
View Article and Find Full Text PDFBackground: Various extensions of the supraorbital approach reach the lateral and parasellar middle cranial fossa regions by removing the orbital rim and greater/lesser sphenoid wings. Recent proposals of a purely endoscopic ventral transorbital pathway to these regions heighten the need to compare these surgical windows.
Objective: To detail the lateral and parasellar middle cranial fossa regions and quantify exposures by 2 surgical windows (transcranial and transorbital) through anatomic study.
Background: The optimal management of tuberculum sellae (TS) meningiomas, especially the surgical strategy, continues to be debated along with several controversies that persist.
Methods: A task force was created by the EANS skull base section committee along with its members and other renowned experts in the field to generate recommendations for the surgical management of these tumors on a European perspective. To achieve this, the task force also reviewed in detail the literature in this field and had formal discussions within the group.
This study provides updated information on the distribution of the phlebotomine sand fly species and their genetic characterization in Sardinia, a Mediterranean island where leishmaniasis is endemic. From April to November 2017, sand flies were trapped in five different capture sites using sticky traps and light traps as collection methods, operated nearby sheep, poultry, cat, and dog shelters. Phlebotomine specimens (n = 513) collected were morphologically and molecularly identified as Phlebotomus perniciosus (249/513, 48.
View Article and Find Full Text PDFTwo very rare cases of barium boryloxides, the homoleptic [Ba(OB{CH(SiMe ) } ) ⋅C H ] and the heteroleptic [{LO }BaOB{CH(SiMe ) } ] stabilised by the multidentate aminoetherphenolate {LO } , are presented, and their structural properties are discussed. The electron-deficient [Ba(OB{CH(SiMe ) } ) ⋅C H ] shows, in particular, resilient η -coordination of the toluene molecule. Together with its amido parents [Ba{N(SiMe ) } ⋅thf ] and [Ba{N(SiMe ) } ] , this complex catalyses the fast and chemoselective dehydrocoupling of borinic acids R BOH and hydrosilanes HSiR' , yielding borasiloxanes R BOSiR' in a controlled fashion.
View Article and Find Full Text PDFA series of methyl aluminum complexes bearing chiral biphenol-type ligands were found to be highly active catalysts in the asymmetric reduction of heterocyclic ketones (S/C = 100-500, ee up to 99%). The protocol is suitable for a wide range of substrates and has a high tolerance to functional groups. The formed 2-heterocyclic-alcohols are valuable building blocks in drug discovery or can be used as ligands in asymmetric catalysis.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2019
Asymmetric catalysis with readily available, cheap, and non-toxic alkaline earth metal catalysts represents a sustainable alternative to conventional synthesis methodologies. In this context, we describe the development of a first Mg -catalyzed enantioselective hydroboration providing the products with excellent yields and enantioselectivities. NMR spectroscopy studies and DFT calculations provide insights into the reaction mechanism and the origin of the enantioselectivity which can be explained by a metal-ligand cooperative catalysis pathway involving a non-innocent ligand.
View Article and Find Full Text PDFSingle atom catalysis (SAC) is a recent discipline of heterogeneous catalysis for which a single atom on a surface is able to carry out various catalytic reactions. A kind of revolution in heterogeneous catalysis by metals for which it was assumed that specific sites or defects of a nanoparticle were necessary to activate substrates in catalytic reactions. In another extreme of the spectrum, surface organometallic chemistry (SOMC), and, by extension, surface organometallic catalysis (SOMCat), have demonstrated that single atoms on a surface, but this time with specific ligands, could lead to a more predictive approach in heterogeneous catalysis.
View Article and Find Full Text PDFBackground: Endoscopic third ventriculostomy is an established treatment for non-communicating hydrocephalus. In carefully selected patients, it can be adopted for the management of communicating variant; however controversy exists in regards to the definition of the appropriate candidates. Predictive score of Endoscopic Third Ventriculostomy Success (ETVSS) has been reported for pediatric and mixed populations only.
View Article and Find Full Text PDFJ Pediatr Gastroenterol Nutr
January 2020
Objectives: The aim of the study was to assess neurodevelopmental outcomes among children with biliary atresia (BA) surviving with their native liver at ages 3 to 12 years and evaluate variables that associate with neurodevelopment.
Methods: Participants (ages 3-12 years) in a prospective, longitudinal, multicenter study underwent neurodevelopmental testing with Weschler Preschool and Primary Scale of Intelligence, 3rd edition (WPPSI-III, ages 3-5 years) and Weschler Intelligence Scale for Children, 4th edition (WISC-IV, ages 6-12 years). Continuous scores were analyzed using Kolmogorov-Smironov tests compared with a normal distribution (mean = 100 ± 15).
The engineering of catalysts with desirable properties can be accelerated by computer-aided design. To achieve this aim, features of molecular catalysts can be condensed into numerical descriptors that can then be used to correlate reactivity and structure. Based on such descriptors, we have introduced topographic steric maps that provide a three-dimensional image of the catalytic pocket-the region of the catalyst where the substrate binds and reacts-enabling it to be visualized and also reshaped by changing various parameters.
View Article and Find Full Text PDFWe report key results of a systematic computational investigation using density functional theory along with the two standard Perdew-Burke-Ernzerhof and hybrid Heyd-Scuseria-Ernzerhof (HSE06) exchange-correlation formalisms on essential fundamental parameters for solar energy conversion of a series of large, medium, and small selected (covalent, binary, and ternary) materials widely utilized in fuel cells, photocatalysis, optoelectronics, photovoltaics, and dye-sensitized solar devices such as BN, AlN, C, ZrO, NaTaO, BiTiO, ZnS, GaN, SrTiO, TiO, BiTiO, SiC, WO, TaON, ZnSe, BiVO, CuNbO, CdS, AlP, ZnTe, GaP, CuO, AlAs, TaN, BP, CdSe, SnWO, GaAs, CdTe, and Si. Our calculations highlight that the optoelectronic and redox parameters computed with HSE06 reproduce with very good accuracy the experimental results, thanks to precise electronic structure calculations. Applying this first-principle quantum methodology led us to provide a rational design of new suitable solid solution materials for visible light-driven photochemical water splitting.
View Article and Find Full Text PDFObjective: Treatment of cystic craniopharyngiomas can be challenging and recurrences are frequent, even after total resection. In selected cases, less-aggressive surgery with the sole drainage of the cyst reliefs symptoms caused by mass effect and represents a valid alternative option, notably in pediatric population. We herein analyze a series of adult cystic craniopharyngiomas, managed with Ommaya Reservoir implant, focusing on local tumor control and eventual complications.
View Article and Find Full Text PDFPurpose: Pituitary adenomas are among the most frequent intracranial tumors. They may exhibit clinically aggressive behavior, with recurrent disease and resistance to multimodal therapy. The ki-67 labeling index represents a proliferative marker which correlates with pituitary adenoma aggressiveness.
View Article and Find Full Text PDFBackground: Tumors involving the sellar area often cause visual disorders due to optic nerves/chiasm compression, so that surgery is required. However, the likelihood of visual improvement/restoration is variable. Optical coherence tomography (OCT) is a valid diagnostic tool for defining pathological conditions of the optic apparatus.
View Article and Find Full Text PDFBackground: Endoscopic skull-base surgery (ESBS) is employed in the management of diverse skull-base pathologies. Paralleling the increased utilization of ESBS, the literature in this field has expanded rapidly. However, the rarity of these diseases, the inherent challenges of surgical studies, and the continued learning curve in ESBS have resulted in significant variability in the quality of the literature.
View Article and Find Full Text PDFFive new complexes [RuCl(SIMes)(Ind)(O-pXCH)] bearing different para-substituted triphenylphosphites (X = H, OCH, CF, Cl, SF and CN) were synthesised and used to study the effect of the electronic properties of the phosphite on olefin metathesis activity. Investigations of the physical properties of the new ligands and complexes were performed using physicochemical and DFT calculations. The catalytic activity of the complexes was benchmarked in challenging ring closing metathesis transformations featuring the formation of tetra-substituted double bonds.
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