Luminescent lanthanide (Ln(III)) complexes with coumarin or carbostyril antennae were synthesized and their photophysical properties evaluated using steady-state time-resolved UV–vis spectroscopy. Ligands bearing distant hydroxycoumarin-derived attached through triazole linkers modest sensitizers for Eu(III) Tb(III), whereas ligands 7-amidocarbostyrils directly linked to the coordination site could reach good quantum yields multiple Ln(III), including visible emitters Sm(III) Dy(III),...

The quenching of sensitized Eu(III) luminescence by photoinduced electron transfer from the excited light-harvesting antenna to was investigated. A series complexes incorporating different metal binding sites and thus having varying Eu(III)/Eu(II) reduction potentials were prepared. fully characterized using a combination single-crystal X-ray crystallography paramagnetic 1H NMR spectroscopy, results which support structural similarity complexes. redox photophysical behavior center studied...

Abstract Controlled, photocatalytic C−H bond activations are key reactions in the toolkits of modern synthetic chemist. While it is known that uranyl(VI) ion, [U VI O 2 ] 2+ , environmentally dominant form uranium, photoactive, most literature examines its luminescent properties, neglecting potential utility for cleavage. Here, we synthesise and fully characterise an air‐stable hydrocarbon‐soluble uranyl phenanthroline complex, (NO 3 ) (Ph phen)], U Ph2phen demonstrate can catalytically...

Obstructive sleep apnoea (OSA) is one of the major sources excessive daily sleepiness, cognitive dysfunction, and it increases cardiovascular morbidity mortality. Previous studies suggested a possible genetic influence, based on questionnaires but no objective study was conducted to understand exact variance underpinned by factors. Seventy-one Hungarian twin pairs involved from Twin Registry (48 monozygotic, MZ 23 dizygotic, DZ pairs, mean age 51 ± 15 years) underwent overnight...

We report a family of lanthanide(III) complexes that act as redox probes via both magnetic resonance and luminescence outputs. The ligands are functionalized with nitro, azobenzene azide groups which reduced to common aniline product, each responds chemical biocatalytic reductive conditions at different cathodic onset potentials. By judicious choice complexed Ln(III), the can be optimized either for use in imaging (Ln = Gd), or highly efficient turn‐on Tb). Tb(III) analogues essentially...

Fluorescence signal enhancement via isothermal nucleic acid amplification is an important approach for sensitive imaging of intra- or extracellular protein biomarkers. Rolling circle (RCA) frequently applied fluorescence in situ but faces limitations concerning multiplexing, dynamic range, and the required multiple washing steps before imaging. Here, we show that Förster resonance energy transfer (FRET) between fluorescent dyes lanthanide (Ln) complexes hybridize to β-actin-specific RCA...

The replacement of the secondary amide linker that carries sensitizing carbostyril antenna with a tertiary in luminescent Eu and Tb complexes dramatically increases lanthanide emission quantum yields.

Azide- and alkyne-functionalized bioconjugable luminescent lanthanide complexes are reported. Reactive handles were introduced into the by late-stage modification of a methylenecarboxylic acid antenna pendent group. Tb Eu quantum yields (11-13% 3.4-3.6%, respectively) not greatly affected presence azide or alkyne compared to parent complex (ΦTb = 10%, ΦEu 2.8%). Two avenues explored for improving luminescence (Ln) complexes: (1) attaching through tertiary amide linker (2) replacing...

Yb(III) complexes of macrocyclic ligands based on 1,4,7,10-tetraazacyclododecane were synthesized. The carried a carbostyril chromophore for sensitization, and carboxylate or carbamide donors metal binding, forming 0, +1, +2, +3 overall charge. coordination geometry was little affected by the replacement carboxylates with amides, as shown paramagnetic 1H NMR spectroscopy. Yb(III)/Yb(II) reduction potentials dependent nature binding site, more positively charged easier to reduce. Carbostyril...

Directly linked hydroporphyrin (chlorin) dimers were accessed regioselectively from bromochlorins. Versatile 15-borylated chlorins prepared in excellent yield via Miyaura borylation. Suzuki coupling yielded meso-meso-linked homo- and heterodimers, meso-β-linked dimers. The photophysical electrochemical properties of the are reported.

Anatomic variants of the circle Willis (CW) are commonly observed in healthy subjects. Genetic and environmental factors influencing these remain unclear. Our aim was to assess genetic background affecting variant CW phenotypes.A total 122 adult twins from Hungarian Twin Registry (39 monozygotic (MZ) 22 dizygotic (DZ) pairs, average age 49.7 ± 13.4 years) underwent Time-of-Flight magnetic resonance angiography transcranial Doppler sonography. We investigated anterior posterior according...

The coordination compounds of the trivalent lanthanide ions (Ln(III)) have unique photophysical properties. Ln(III) excitation is usually performed through a light-harvesting antenna. To enable Ln(III)-based emitters to reach their full potential, an understanding how complex structure affects sensitization and quenching processes necessary. Here, role linker between antenna metal binding fragment was studied. Four macrocyclic ligands carrying coumarin 2 or 4-methoxymethylcarbostyril...

Luminescent Eu(III)- and Tb(III)-complexes based on functionalized tetraazamacrocycle (cyclen) or dipicolinic acid (dpa) metal binding sites, carrying 2′- 5′-linked uridine moieties were prepared. The light-harvesting antennae either a coumarin (in the cyclen-based architectures) dpa-moiety itself. Antenna excitation resulted in metal-centered emission for all complexes. presence of less intense lanthanide compared to non-nucleotide-modified reference compounds. Nd(III)-complexes cyclen...

Background: Periacetabular osteotomy (PAO) is the standard of care for treatment symptomatic acetabular dysplasia. Patients undergoing PAO dysplasia have postoperative pain that can be managed with epidural analgesia. The purpose this study was to evaluate impact timing discontinuation analgesia on pain, opioid usage, and hospital length stay (LOS). hypothesis removal catheter day 1 (POD1) would lead reduced overall usage LOS compared POD2. Methods: This a retrospective before-and-after...

A series of luminescent lanthanide(<sc>iii</sc>) complexes consisting 1,4,7-triazacyclononane-1,4-picolinate frameworks and three secondary amidelinked carbostyril antennae were synthesised characterised.

Background: The effects of ischemic preconditioning (IPC) versus a deceptive sham protocol on indirect markers exercise-induced muscle damage (EIMD) after the application individualized occlusion pressure were examined. goal using is to control for potential effect placebo. Hypothesis: IPC would surpass in protecting against EIMD. Study Design: A randomized, double-blinded, clinical trial. Level Evidence: 1. Methods: Thirty healthy young men randomly assigned an eccentric exercise knee...

The reaction of various anthranilic acid derivatives or their esters with 4-oxotetrahydrothiophene-3-carbonitrile 2, 2-oxocyclopentanecarbonitrile (9, n = 1) 2-oxocyclohexanecarbonitrile 2) in ethanol under reflux conditions giving rise the formation single products isolated each case after simple filtration. were characterized as pyrazolo[1,5-a]quinazolin-5-ones 4 instead expected pyrazol-3-amines 3. These cascade condensation–intramolecular acylation processes generated one-step reactions...

Luminescent Eu(III) and Tb(III) complexes were synthesised from octadentate ligands carrying various carbostyril sensitizing antennae two bidentate picolinate donors. Antennae connected to the metal binding site via tertiary amide linkers. donors assembled on a 1,4,7-triazacyclononane (tacn) platform. Solution- solid-state structures comparable those of previously reported with tacn architectures, nine-coordinate distorted tricapped trigonal prismatic Ln(III) centres, distinct based...

Yb(III) complexes based on ligands with a 1,4,7-triazacyclononane (tacn) macrocyclic core were synthesised. The carry 4-methoxymethyl-substituted carbostyril chromophore that serves as light-harvesting antenna. supply 5 nitrogen and 3 oxygen donors via 1 methylenecarboxamide 2 picolinate donors, creating +1 charged an octadentate binding environment. electronic properties of the picolinates are modulated by varying substitution at 4 position OMe, H, Cl, or CF3. Cyclic voltammetry indicated...

A simple protocol for the controlled preparation of mono‐ and diprotonated hydroporphyrins (chlorins) is presented. The chlorins carried 10‐aryl groups with electron‐neutral (phenyl), electron‐donating ( p ‐OMe‐C 6 H 4 ) or electron‐withdrawing (pentafluorophenyl) substituents. protonation reactions were readily followed by UV/Vis absorption spectroscopy, enabling determination first (4.8–5.3) second K a 's (1.7–0.5). Both species fully characterized 1 NMR which, in combination theoretical...

Abstract Four triazamacrocyclic and two tetraazamacrocyclic ligands carrying three coordinating donor groups, respectively, a carbostyril light‐harvesting antenna were synthesized. The was linked to macrocycle either via secondary or tertiary amide. Complexation with europium (Eu), gadolinium (Gd), terbium (Tb), ytterbium (Yb) yielded overall +1 +2 charged species. Paramagnetic 1 H NMR, steady‐state time‐resolved luminescence spectroscopies showed that the complexes had 1–3 inner‐sphere...

Background: Ischemic preconditioning (IPC) has been used to improve exercise performance, but its role in protecting against exercise-induced muscle damage (EIMD) is still unclear. Objective: To investigate the effects of IPC on indirect markers EIMD when compared placebo. Methods: 30 healthy young men, with no recent experience lower limb strength training, will be recruited. Subjects allocated randomly into two groups: or The group undergo 4 x 5 min occlusion (with individualized total...

Abstract Previous studies suggested cervical spondylosis as a risk factor for development of obstructive sleep apnoea (OSA). We aimed to assess lumbar disc degeneration in patients with OSA and correlate the findings symptoms disease severity. Twenty-seven 29 non-OSA controls underwent magnetic resonance imaging (MRI), completed Epworth Sleepiness Scale 24-item Roland‐Morris Disability Questionnaire questionnaires. Plasma klotho was determined enzyme-linked immunosorbent assay.Patients had...