Modern possibilities of neurosurgical treatment of brain metastases.

Despite significant progress in neuroimaging and introduction of new combined treatments for solid tumors, brain metastases are still adverse factor for overall survival. Brain metastases are diagnosed in 8-10% of patients and associated with extremely poor prognosis. These lesions result focal and general cerebral symptoms.

Craniopharyngiomas: Surgery and Radiotherapy.

Taking into account the benign nature of craniopharyngiomas, the main method of treatment is the resection of the tumor. However, the tendency of these tumors to invade critical structures (such as optic pathways, the hypothalamic-pituitary system, the Willis circle vessels) often limits the possibility of a radical surgery.Craniopharyngiomas of the third ventricle represent the greatest challenge for surgery.

[Stereotactic radiosurgery for epilepsy related to hypothalamic hamartoma].

Unlabelled: Hypothalamic hamartoma (HH) is a dysplastic lesion fused with hypothalamus and followed by epilepsy, precocious puberty and behavioral disorders. Up to 50% of patients become free of seizures after surgery, but various complications occur in 1/4 of cases. Radiofrequency thermocoagulation, laser interstitial thermal therapy and stereotactic radiosurgery (SRS) are alternative treatment options.

Discrepancies between frame- and CBCT-based stereotactic space definition on the Gamma Knife Icon.

Purpose: To assess differences between frame-based and cone beam computed tomography (CBCT)-defined stereotactic space and to identify predictors of the observed findings.

Methods And Materials: Differences between frame-based and CBCT-defined stereotactic space after image co-registration were reviewed for 529 patients. Treatment planning system reported the information about the shifts in X, Y, and Z coordinates of the center of the stereotactic space (i.

Progress in Development of Photocatalytic Processes for Synthesis of Fuels and Organic Compounds under Outdoor Solar Light.

With photovoltaics becoming a mature, commercially feasible technology, society is willing to allocate resources for developing and deploying new technologies based on using solar light. Analysis of projects supported by the European Commission in the past decade indicates exponential growth of funding to photocatalytic (PC) and photoelectrocatalytic (PEC) technologies that aim either at technology readiness levels (TRLs) TRL 1-3 or TRL > 3, with more than 75 Mio€ allocated from the year 2019 onward. This review provides a summary of PC and PEC processes for the synthesis of bulk commodities such as solvents and fuels, as well as chemicals for niche applications.

Saving the Energy Loss in Lithium-Mediated Nitrogen Fixation by Using a Highly Reactive Li N Intermediate for C-N Coupling Reactions.

Direct synthesis of N-containing organic compounds from dinitrogen (N ) can make synthetic chemistry more sustainable. Previous bottlenecks in lithium-mediated N fixation were resolved by loading Li-metal anodes covered with the typical Li ion-conducting solid electrolyte interface, which are subsequently allowed to react with N . The developed strategy allowed us to reach high Faradaic efficiencies toward Li N.

Red edge effect and chromoselective photocatalysis with amorphous covalent triazine-based frameworks.

Chromoselective photocatalysis offers an intriguing opportunity to enable a specific reaction pathway out of a potentially possible multiplicity for a given substrate by using a sensitizer that converts the energy of incident photon into the redox potential of the corresponding magnitude. Several sensitizers possessing different discrete redox potentials (high/low) upon excitation with photons of specific wavelength (short/long) have been reported. Herein, we report design of molecular structures of two-dimensional amorphous covalent triazine-based frameworks (CTFs) possessing intraband states close to the valence band with strong red edge effect (REE).

Mesoporous Graphitic Carbon Nitride as a Heterogeneous Organic Photocatalyst in the Dual Catalytic Arylation of Alkyl Bis(catecholato)silicates.

Mesoporous graphitic carbon nitride (mpg-CN) is introduced as a heterogeneous photocatalyst to perform dual photoredox- and nickel-catalyzed cross-coupling reactions between alkyl bis(catecholato)silicates as radical precursors and aryl or alkenyl bromides. The synergy between this recyclable photocatalyst and the broadly applied homogeneous nickel complex [Ni(dtbbpy)Br] gives access to C(sp)-C(sp) cross-coupling products in a sustainable fashion. The recycled mpg-CN photocatalyst was analyzed by time-resolved emission spectroscopy and EPR spectroscopy.

Multisite PCET with photocharged carbon nitride in dark.

A combination of photochemistry and proton coupled electron transfer (PCET) is a primary strategy employed by biochemical systems and synthetic chemistry to enable uphill reactions under mild conditions. Degenerate nanometer-sized n-type semiconductor nanoparticles (SCNPs) with the Fermi level above the bottom of the conduction band are strongly reducing and act more like metals than semiconductors. Application of the degenerate SCNPs is limited to few examples.

Synthesis of Sulfonyl Chlorides from Aryldiazonium Salts Mediated by a Heterogeneous Potassium Poly(heptazine imide) Photocatalyst.

Visible light photocatalysis is a tool in synthetic chemistry that allows us to utilize the energy of photons via photoinduced electron transfer to promote diverse organic reactions. Herein, a heterogeneous transition metal-free material, a type of carbon nitride photocatalyst, potassium poly(heptazine imide), is employed to produce sulfonyl chlorides from arenediazonium salts under mild conditions (visible light irradiation, room temperature) with 50-95% yields. The method is suitable for the synthesis of both electron rich and electron deficient compounds, and it shows high tolerance toward different functional groups (halides, ester, nitro, cyano groups).

[Hepatopulmonary syndrome: a rare manifestation of cirrhosis in patient with diencephalic obesity and nonalcoholic fatty liver disease after surgery for craniopharyngioma].

We describe a 15-year girl, who developed panhypopituitarism and diencephalic obesity after surgical excision of craniopharyngioma, followed by nonalcoholic fatty liver disease and cirrhosis 5 years after surgery. Cirrhosis in this case manifested by hypoxia due to hepatopulmonary syndrome, and despite cure of craniopharyngioma by surgery and radiosurgery treatment and adequate hormonal substitution therapy patient died 9 years after surgery. Growth hormone substitutional therapy in patients with hypopituitarism, and steatohepatitis may decrease liver triglyceride accumulation and prevent end-stage liver disease.

Photocatalytic Water Splitting Reaction Catalyzed by Ion-Exchanged Salts of Potassium Poly(heptazine imide) 2D Materials.

Potassium poly (heptazine imide) (K-PHI), a crystalline two-dimensional carbon-nitride material, is an active photocatalyst for water splitting. The potassium ions in K-PHI can be exchanged with other ions to change the properties of the material and eventually to design the catalysts. We report here the electronic structures of several ion-exchanged salts of K-PHI (K, H, Au, Ru, and Mg) and their feasibility as water splitting photocatalysts, which were determined by density functional theory (DFT) calculations.

Chromoselective Synthesis of Sulfonyl Chlorides and Sulfonamides with Potassium Poly(heptazine imide) Photocatalyst.

Among external stimuli used to promote a chemical reaction, photocatalysis possesses a unique one-light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light.

Laser-driven growth of structurally defined transition metal oxide nanocrystals on carbon nitride photoelectrodes in milliseconds.

Fabrication of hybrid photoelectrodes on a subsecond timescale with low energy consumption and possessing high photocurrent densities remains a centerpiece for successful implementation of photoelectrocatalytic synthesis of fuels and value-added chemicals. Here, we introduce a laser-driven technology to print sensitizers with desired morphologies and layer thickness onto different substrates, such as glass, carbon, or carbon nitride (CN). The specially designed process uses a thin polymer reactor impregnated with transition metal salts, confining the growth of transition metal oxide (TMO) nanostructures on the interface in milliseconds, while their morphology can be tuned by the laser.

Ligand-Metal Charge Transfer Induced Adjustment of Textural Properties Controls the Performance of Single-Atom Catalysts during Photocatalytic Degradation.

Because of their peculiar nitrogen-rich structure, carbon nitrides are convenient polydentate ligands for designing single atom-dispersed photocatalysts. However, the relation between catalysts' textural properties and their photophysical-photocatalytic properties is rarely elaborated. Herein, we report the preparation and characterization of a series of single-atom heterogeneous catalysts featuring highly dispersed Ag and Cu species on mesoporous graphitic CN.

Enhanced Organic Photocatalysis in Confined Flow through a Carbon Nitride Nanotube Membrane with Conversions in the Millisecond Regime.

Bioinspired nanoconfined catalysis has developed to become an important tool for improving the performance of a wide range of chemical reactions. However, photocatalysis in a nanoconfined environment remains largely unexplored. Here, we report the application of a free-standing and flow-through carbon nitride nanotube (CNN) membrane with pore diameters of 40 nm for confined photocatalytic reactions where reactants are in contact with the catalyst for <65 ms, as calculated from the flow.

Solar Reforming of Biomass with Homogeneous Carbon Dots.

A sunlight-powered process is reported that employs carbon dots (CDs) as light absorbers for the conversion of lignocellulose into sustainable H fuel and organics. This photocatalytic system operates in pure and untreated sea water at benign pH (2-8) and ambient temperature and pressure. The CDs can be produced in a scalable synthesis directly from biomass itself and their solubility allows for good interactions with the insoluble biomass substrates.

Unconventional Photocatalysis in Conductive Polymers: Reversible Modulation of PEDOT:PSS Conductivity by Long-Lived Poly(Heptazine Imide) Radicals.

In photocatalysis, small organic molecules are converted into desired products using light responsive materials, electromagnetic radiation, and electron mediators. Substitution of low molecular weight reagents with redox active functional materials may increase the utility of photocatalysis beyond organic synthesis and environmental applications. Guided by the general principles of photocatalysis, we design hybrid nanocomposites composed of n-type semiconducting potassium poly(heptazine imide) (K-PHI), and p-type conducting poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as the redox active substrate.

Emerging Concepts in Carbon Nitride Organic Photocatalysis.

Carbon nitrides encompass a class of transition-metal-free materials possessing numerous advantages such as low cost (few Euros per gram), high chemical stability, broad tunability of redox potentials and optical bandgap, recyclability, and a high absorption coefficient (>10  cm ), which make them highly attractive for application in photoredox catalysis. In this Review, we classify carbon nitrides based on their unique properties, structure, and redox potentials. We summarize recently emerging concepts in heterogeneous carbon nitride photocatalysis, with an emphasis on the synthesis of organic compounds: 1) Illumination-Driven Electron Accumulation in Semiconductors and Exploitation (IDEASE); 2) singlet-triplet intersystem crossing in carbon nitride excited states and related energy transfer; 3) architectures of flow photoreactors; and 4) dual metal/carbon nitride photocatalysis.

[Radiosurgical hypophysectomy in cancer pain treatment. Literature review and clinical case].

Cancer pain is one of the main problem in modern medicine. According European Society for Medical Oncology data, cancer pain prevalence is 64% among patient with terminal stage of disease and in 46% standard pain therapy was ineffective. Radiosurgical hypophysectomy is one of the important and perspective method in cancer pain treatment.

Potassium Poly(Heptazine Imide): Transition Metal-Free Solid-State Triplet Sensitizer in Cascade Energy Transfer and [3+2]-cycloadditions.

Polymeric carbon nitride materials have been used in numerous light-to-energy conversion applications ranging from photocatalysis to optoelectronics. For a new application and modelling, we first refined the crystal structure of potassium poly(heptazine imide) (K-PHI)-a benchmark carbon nitride material in photocatalysis-by means of X-ray powder diffraction and transmission electron microscopy. Using the crystal structure of K-PHI, periodic DFT calculations were performed to calculate the density-of-states (DOS) and localize intra band states (IBS).

Metal-free activation of molecular oxygen by covalent triazine frameworks for selective aerobic oxidation.

Oxygen activation is a critical step in ubiquitous heterogeneous oxidative processes, most prominently in catalysis, electrolysis, and pharmaceutical applications. We present here our findings on metal-free O activation on covalent triazine frameworks (CTFs) as an important class of N-rich materials. The O activation process was studied for the formation of aldehydes, ketones and imines.

Dichloromethylation of enones by carbon nitride photocatalysis.

Small organic radicals are ubiquitous intermediates in photocatalysis and are used in organic synthesis to install functional groups and to tune electronic properties and pharmacokinetic parameters of the final molecule. Development of new methods to generate small organic radicals with added functionality can further extend the utility of photocatalysis for synthetic needs. Herein, we present a method to generate dichloromethyl radicals from chloroform using a heterogeneous potassium poly(heptazine imide) (K-PHI) photocatalyst under visible light irradiation for C1-extension of the enone backbone.

Treatment of Pediatric Glioblastoma with Combination Olaparib and Temozolomide Demonstrates 2-Year Durable Response.

For pediatric patients with high-grade gliomas, standard-of-care treatment includes surgery, chemotherapy, and radiation therapy; however, most patients ultimately succumb to their disease. With advances in genomic characterization of pediatric high-grade gliomas, the use of targeted therapies in combination with current treatment modalities offer the potential to improve survival in this patient population. In this report, we present the case of a 3-year-old girl with glioblastoma who continues to experience an exceptional and durable response (>2 years) to the poly (ADP-ribose) polymerase (PARP) inhibitor olaparib.