It has been suggested that slow oscillations in the subthalamic nucleus (STN) reflect top-down inputs from the medial prefrontal cortex, thus implementing behavior control. It is unclear, however, whether the STN oscillations are related to cortical activity in a bottom-up manner. To assess resting-state subcortico-cortical interactions, we recorded simultaneous scalp electroencephalographic activity and local field potentials in the STN (LFP-STN) in 11 patients with Parkinson's disease implanted with deep brain stimulation electrodes in the on-medication state during rest. We assessed the cross-structural phase-amplitude coupling (PAC) between the STN and cortical activity within a wide frequency range of 1 to 100 Hz. The PAC was dominant between the δ/θ STN phase and β/γ cortical amplitude in most investigated scalp regions and between the δ cortical phase and θ/α STN amplitude in the frontal and temporal regions. The cross-frequency linkage between the slow oscillations of the LFP-STN activity and the amplitude of the scalp-recorded cortical activity at rest was demonstrated, and similar involvement of the left and right STNs in the coupling was observed. Our results suggest that the STN plays a role in both bottom-up and top-down processes within the subcortico-cortical circuitries of the human brain during the resting state. A relative left-right symmetry in the STN-cortex functional linkage was suggested. Practical treatment studies would be necessary to assess whether unilateral stimulation of the STN might be sufficient for treatment of Parkinson's disease.

• Klíčová slova
• Cross-structural coupling, Phase-amplitude coupling, Simultaneous intracranial and scalp EEG, Subcortico-cortical interactions, Subthalamic nucleus,
• MeSH
• elektroencefalografie MeSH
• hluboká mozková stimulace * MeSH
• lidé MeSH
• nucleus subthalamicus * MeSH
• Parkinsonova nemoc * terapie   MeSH
• skalp MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH

Herein, we report the first mechanochemical strategy for the Ru-catalyzed deoxygenative borylation of free phenols via C-O bond cleavage. This Ru-catalyzed phenolic borylation approach has been successfully extended to the Suzuki-Miyaura-type cross-coupling of phenols with aryl bromides. The protocol accepts a wide scope of phenolic substrates, allowing the synthesis of aryl pinacolboranes and biphenyl structures in excellent yields and serving as a better alternative to classical cross-coupling reactions in the context of pot, atom, and step economy synthesis.

• Klíčová slova
• Suzuki–Miyaura-type cross-coupling, borylation, mechanochemistry, phenols, ruthenium,
• Publikační typ
• časopisecké články MeSH

Palladium nanoparticles entrapped in porous aromatic frameworks (PAFs) or covalent organic frameworks may promote heterogeneous catalytic reactions. However, preparing such materials as active nanocatalysts usually requires additional steps for palladium entrapment and reduction. This paper reports as a new approach, a simple procedure leading to the self-entrapment of Pd nanoparticles within the PAF structure. Thus, the selected Sonogashira synthesis affords PAF-entrapped Pd nanoparticles that can catalyze the C-C Suzuki-Miyaura cross-coupling reactions. Following this new concept, PAFs were synthesized via Sonogashira cross-coupling of the tetraiodurated derivative of tetraphenyladamantane or spiro-9,9'-bifluorene with 1,6-diethynylpyrene, then characterized them using powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, X-ray photoelectron spectroscopy, high-resolution scanning transmission electron microscopy, and textural properties (i.e., adsorption-desorption isotherms). The PAF-entrapped Pd nanocatalysts showed high catalytic activity in Suzuki-Miyaura coupling reactions (demonstrated by preserving the turnover frequency values) and stability (demonstrated by palladium leaching and recycling experiments). This new approach presents a new class of PAFs with unique structural, topological, and compositional complexities as entrapped metal nanocatalysts or for other diverse applications.

• Klíčová slova
• 1,6-diethynylpyrene, STEM characterization of PAFs, Sonogashira synthesis of PAFs, Suzuki−Miyaura cross-coupling, heterogeneous catalysts, spiro-9,9′-bifluorene, tetraphenyladamantane-based PAFs,
• Publikační typ
• časopisecké články MeSH

In this review, we emphasize the significance of the Liebeskind-Srogl cross-coupling reaction, a palladium-catalyzed process involving the reaction between a thioester and a boronic acid. This reaction has emerged as a fundamental technique in synthetic methodologies aimed at the development of biologically active compounds. The Liebeskind-Srogl cross-coupling method has become an essential approach in chemistry, facilitating the diversification of complex structures that would be significantly more challenging to synthesize through alternative approaches. In this review, we aim to outline the numerous possibilities for preparing a wide range of derivatives, each with notable biological potential.

• Klíčová slova
• Biological activity, Catalysis, Copper, Cross-coupling, C–C bond formation, Heterocycles, Libeskind-Srogl, Medicinal chemistry, Natural products, Organometallic, Organosulfur, Palladium,
• MeSH
• katalýza MeSH
• kyseliny boronové * chemie   MeSH
• molekulární struktura MeSH
• palladium chemie   MeSH
• techniky syntetické chemie * metody   MeSH
• Publikační typ
• časopisecké články MeSH
• přehledy MeSH
• Názvy látek
• kyseliny boronové * MeSH
• palladium MeSH

OBJECTIVES: This cross-sectional analysis from the CZecking Heart Failure in patients with advanced Chronic Kidney Disease trial (ISRCTN18275480) examined pulmonary hypertension and right ventricular-pulmonary arterial coupling in patients on chronic hemodialysis. The aims of this analysis were: 1. To analyze relations between pulmonary hypertension and right ventricular-pulmonary arterial coupling with dialysis access flow and current hydration; 2. To analyze structural heart changes associated with right ventricular-pulmonary arterial uncoupling; 3. To reveal the prevalence, etiology and severity of pulmonary hypertension in the Czech hemodialysis population. METHODS: We performed expert echocardiography, vascular access flow measurements, bioimpedance analysis, and laboratory testing in 336 hemodialysis patients. RESULTS: Pulmonary hypertension was present in 34% (114/336) patients and right ventricular-pulmonary arterial uncoupling was present in 25% of patients with pulmonary hypertension. Only weak associations between the flow of the dialysis arteriovenous access and estimated pulmonary arterial systolic pressure and right ventricular-pulmonary arterial coupling was proved. There was a strong association between hydration status assessed by estimated central venous pressure with pulmonary arterial systolic pressure (Rho 0.6, p < 0.0001) and right ventricular-pulmonary arterial coupling (Rho -0.52, p < 0.0001) and association between overhydration to extracellular water ratio with pulmonary arterial systolic pressure (Rho 0.31, p = 0.0001) and right ventricular-pulmonary arterial coupling (Rho -0.29, p = 0.002). The prevalence of heart failure was significantly higher in patients with right ventricular-pulmonary arterial uncoupling (88% vs. 52%, p = 0.0003). CONCLUSION: These findings suggest that optimizing volume status and treating heart failure should be prioritized in hemodialysis patients to prevent pulmonary hypertension progression and right ventricular-pulmonary arterial uncoupling.

• Klíčová slova
• Right ventricular-pulmonary arterial coupling, arteriovenous access flow, chronic hemodialysis, fluid overload, heart failure, pulmonary hypertension,
• MeSH
• arteria pulmonalis * patofyziologie   diagnostické zobrazování   MeSH
• chronické selhání ledvin * terapie   komplikace   MeSH
• dialýza ledvin * škodlivé účinky   MeSH
• echokardiografie MeSH
• lidé středního věku MeSH
• lidé MeSH
• plicní hypertenze * patofyziologie   epidemiologie   etiologie   MeSH
• prevalence MeSH
• průřezové studie MeSH
• senioři MeSH
• srdeční komory * patofyziologie   diagnostické zobrazování   MeSH
• Check Tag
• lidé středního věku MeSH
• lidé MeSH
• mužské pohlaví MeSH
• senioři MeSH
• ženské pohlaví MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• Česká republika epidemiologie   MeSH

The synthesis of the title 2'-deoxyadenosine derivatives bearing bipyridine, phenanthroline or terpyridine ligands and their corresponding RuII-complexes in position 8 linked via acetylene or phenylene tethers was accomplished through cross-coupling reactions. The Suzuki-Miyaura reactions of boronic acids or the Sonogashira reactions of terminal acetylene derivatives of oligopyridine ligands were performed either on protected 8-bromoadenosines in organic solvents or, more efficiently, directly on unprotected nucleosides in aqueous acetonitrile or DMF. Direct cross-coupling reactions of unprotected nucleosides with RuII-complexes or the oligopyridine-boronic acids or -acetylenes gave the Ru-labelled nucleosides in one step in fair to good yields. This method was also proven to be applicable for direct Ru-labelling of dATP. Terpyridine-containing 2'-deoxyadenosine exerted significant antiviral and cytostatic effects.

• MeSH
• antivirové látky chemická syntéza   chemie   toxicita   MeSH
• deoxyadenosiny chemická syntéza   chemie   toxicita   MeSH
• difrakce rentgenového záření MeSH
• Hepacivirus účinky léků   MeSH
• ligandy MeSH
• molekulární modely MeSH
• molekulární struktura MeSH
• protinádorové látky chemická syntéza   chemie   toxicita   MeSH
• pyridiny chemie   MeSH
• reagencia zkříženě vázaná chemie   MeSH
• sloučeniny ruthenia chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• 2'-deoxyadenosine MeSH Prohlížeč
• antivirové látky MeSH
• deoxyadenosiny MeSH
• ligandy MeSH
• protinádorové látky MeSH
• pyridiny MeSH
• reagencia zkříženě vázaná MeSH
• sloučeniny ruthenia MeSH

NiII(IB) dihalide [IB = (3aR,3a'R,8aS,8a'S)-2,2'-(cyclopropane-1,1-diyl)bis(3a,8a-dihydro-8H-indeno[1,2-d]-oxazole)] complexes are representative of a growing class of first-row transition-metal catalysts for the enantioselective reductive cross-coupling of C(sp2) and C(sp3) electrophiles. Recent mechanistic studies highlight the complexity of these ground-state cross-couplings but also illuminate new reactivity pathways stemming from one-electron redox and their significant sensitivities to reaction conditions. For the first time, a diverse array of spectroscopic methods coupled to electrochemistry have been applied to NiII-based precatalysts to evaluate specific ligand field effects governing key Ni-based redox potentials. We also experimentally demonstrate DMA solvent coordination to catalytically relevant Ni complexes. Coordination is shown to favorably influence key redox-based reaction steps and prevent other deleterious Ni-based equilibria. Combined with electronic structure calculations, we further provide a direct correlation between reaction intermediate frontier molecular orbital energies and cross-coupling yields. Considerations developed herein demonstrate the use of synergic spectroscopic and electrochemical methods to provide concepts for catalyst ligand design and rationalization of reaction condition optimization.

• Publikační typ
• časopisecké články MeSH

A new type of robust, heterogeneous, modular Pd catalyst with metal embedded in the gel matrix is presented. The regulatory element of its catalytic activity has been introduced via chemical changes in the gel. The concept is illustrated in a series of Suzuki-Miyaura cross-coupling reactions. The demonstrated catalyst activity variations depend on the structure of the gel.

• MeSH
• gely chemie   MeSH
• katalýza MeSH
• molekulární struktura MeSH
• palladium chemie   MeSH
• vztahy mezi strukturou a aktivitou MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• gely MeSH
• palladium MeSH

4,4-Difluoro-4-borata-3a-azonia-4a-aza-s-indacene (BODIPY) dyes are extensively used in various applications of their triplet states, ranging from photoredox catalysis, through triplet sensitization to photodynamic therapy. However, the rational design of BODIPY triplet chromophores by ab initio modelling is limited by their strong interactions of spin, electronic and vibrational dynamics. In particular, spin-vibronic coupling is often overlooked when estimating intersystem crossing (ISC) rates. In this study, a combined experimental and theoretical approach using spin-vibronic coupling to correctly describe ISC in BODIPY dyes was developed. For this purpose, seven π-extended BODIPY derivatives with iodine atoms in different positions were examined. It was found that the heavy-atom effect of iodine atoms is site specific, causing high triplet yields in only some positions. This site-specific ISC was explained by El-Sayed rules, so both the contribution and character of the molecular orbitals involved in the excitation must be considered when predicting the ISC rates. Overall, the rational design of BODIPY triplet chromophores requires using (i) the high-quality electronic structure theory, including both static and dynamical correlations; and (ii) the two-component wave function Hamiltonian, and rationalizing; and (iii) ISC based on the character of the molecular orbitals of heavy atoms involved in the excitation, expanding El-Sayed rules beyond their traditional applications.

• Klíčová slova
• BODIPYs, El-Sayed rules, intersystem crossing, spin-vibronic couplings, triplet chromophores,
• Publikační typ
• časopisecké články MeSH

A nanomagnetic hydrophilic heterogeneous copper catalyst, termed γ-Fe2O3@PEG@PAMAM G0-Cu, has been successfully prepared and characterized using FT-IR, XRD, FE-SEM, TEM, EDX, mapping, TGA/DTG, VSM and ICP analyses. The catalyst displayed excellent activity for the palladium-free Sonogashira cross coupling reaction of various aryl iodides and bromides with phenylacetylene derivatives in pure water. The presence of polyethylene glycol coupled with hydrophilic character of the Cu-catalyst adorned on γ-Fe2O3 MNPs provides the ready dispersion of the catalyst particles in water, leading to higher catalytic performance as well as facile catalyst recovery via simple magnetic decantation. The recovered catalyst was reused for at least six successive runs with little reduction in its catalytic activity and any noticeable changes in its structure. The use of water as a green solvent, without requiring any additive or organic solvent, as well as the exploitation of abundant and low-cost copper catalyst instead of expensive Pd catalyst along with the catalyst recovery and scalability, make this method favorable from environmental and economic points of view for the Sonogashira coupling reaction.

• MeSH
• bromidy MeSH
• jodidy MeSH
• magnetické nanočástice * MeSH
• měď * chemie   MeSH
• polyethylenglykoly MeSH
• rozpouštědla MeSH
• spektroskopie infračervená s Fourierovou transformací MeSH
• voda MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• bromidy MeSH
• jodidy MeSH
• magnetické nanočástice * MeSH
• měď * MeSH
• polyethylenglykoly MeSH
• rozpouštědla MeSH
• voda MeSH