Identification of Mycobacterium abscessus Subspecies by MALDI-TOF Mass Spectrometry and Machine Learning.

Mycobacterium abscessus is one of the most common and pathogenic nontuberculous mycobacteria (NTM) isolated in clinical laboratories. It consists of three subspecies: M. abscessus subsp. abscessus, M. abscessus subsp. bolletii, and M. abscessus subsp. massiliense. Due to their different antibiotic susceptibility pattern, a rapid and accurate identification method is necessary for their differentiation. Although matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS) has proven useful for NTM identification, the differentiation of M. abscessus subspecies is challenging. In this study, a collection of 325 clinical isolates of M. abscessus was used for MALDI-TOF MS analysis and for the development of machine learning predictive models based on MALDI-TOF MS protein spectra. Overall, using a random forest model with several confidence criteria (samples by triplicate and similarity values >60%), a total of 96.5% of isolates were correctly identified at the subspecies level. Moreover, an improved model with Spanish isolates was able to identify 88.9% of strains collected in other countries. In addition, differences in culture media, colony morphology, and geographic origin of the strains were evaluated, showing that the latter had an impact on the protein spectra. Finally, after studying all protein peaks previously reported for this species, two novel peaks with potential for subspecies differentiation were found. Therefore, machine learning methodology has proven to be a promising approach for rapid and accurate identification of subspecies of M. abscessus using MALDI-TOF MS.

Laser Cutting Coupled with Electro-Exfoliation to Prepare Versatile Planar Graphene Electrodes for Energy Storage.

The study of planar energy storage devices, characterized by low-cost, high capacity, and satisfactory flexibility, is becoming a valuable research hotspot. Graphene, monolayer sp2 hybrid carbon atoms with a large surface area, always acts as its active component, yet there is a tension between its high conductivity and ease of implementation. Although the difficult-to-assemble graphene can easily achieve planar assemblies in its highly oxidized form (GO), the undesirable conductivity, even after proper reduction, still restricts its further applications. Here, a facile "Top-down" method has been proposed to prepare the graphene planar electrode via in situ electro-exfoliation of graphite supported on a piece of laser-cutting patterned scotch tape. Detailed characterizations have been performed to study its physiochemical property evolution during electro-exfoliation. The obtained flexible graphene planar electrodes show decent energy storage performance, e.g., 40.8 mF cm-2 at a current density of 0.5 mA cm-2 and an 81% capacity retention at a current density of 8 mA cm-2 for the optimized sample G-240. Their high conductivity also makes it possible to couple them with other redox-active materials through electrodeposition to improve their performance, e.g., ferrocene-functionalized mesoporous silica film (Fc-MS), MnO2, and polyaniline (PANI). The highest capacity was achieved with the PANI functionalized sample, which achieved a 22-fold capacity increase. In a word, the versatility, practicality, and adaptability of the protocol to prepare the planar graphene electrode proposed in this work make it a potential candidate to meet the continuously growing energy storage demands.

Polyaniline nanowire arrays generated through oriented mesoporous silica films: effect of pore size and spectroelectrochemical response.

Indium-tin oxide electrodes modified with vertically aligned silica nanochannel membranes have been produced by electrochemically assisted self-assembly of cationic surfactants (cetyl- or octadecyl-trimethylammonium bromide) and concomitant polycondensation of the silica precursors (tetraethoxysilane). They exhibited pore diameters in the 2-3 nm range depending on the surfactant used. After surfactant removal, the bottom of mesopores was derivatized with aminophenyl groups via electrografting (i.e., electrochemical reduction of in situ generated aminophenyl monodiazonium salt). These species covalently bonded to the ITO substrate were then exploited to grow polyaniline nanofilaments by electropolymerization of aniline through the nanochannels. Under potentiostatic conditions, the length of polyaniline wires is controllable by tuning the electropolymerization time. From cyclic voltammetry characterization performed either before or after dissolution of the silica template, it appeared that both the polyaniline/silica composite and the free polyaniline nanowire arrays were electroactive, yet with much larger peak currents in the latter case as a result of larger effective surface area offered to the electrolyte solution. At identical electropolymerization time, the amount of deposited polyaniline was larger when using the silica membrane with larger pore diameter. All polyaniline deposits exhibited electrochromic properties. However, the spectroelectrochemical data indicated more complete interconversion between the coloured oxidized form and colourless reduced polyaniline for the arrays of nanofilaments in comparison to bulky films. In addition, the template-free nanowire arrays (i.e., after silica dissolution) were characterized by faster electrochromic behaviour than the polyaniline/silica hybrid, confirming the potential interest of such polyaniline nano-brushes for practical applications.

Weak Coordinating Character of Organosulfonates in Oriented Silica Films: An Efficient Approach for Immobilizing Cationic Metal-Transition Complexes.

Iron (II) tris(2,2'-bipyridine) complexes, [Fe(bpy)3]2+, have been synthesized and immobilized in organosulfonate-functionalized nanostructured silica thin films taking advantage of the stabilization of [Fe(H2O)6]2+ species by hydrogen bonds to the anionic sulfonate moieties grafted to the silica nanopores. In a first step, thiol-based silica films have been electrochemically generated on indium tin oxide (ITO) substrates by co-condensation of 3-mercaptopropyltrimethoxysilane (MPTMS) and tetraethoxysilane (TEOS). Secondly, the thiol function has been modified to sulfonate by chemical oxidation using hydrogen peroxide in acidic medium as an oxidizing agent. The immobilization of [Fe(bpy)3]2+ complexes has been performed in situ in two consecutive steps: (i) impregnation of the sulfonate functionalized silica films in an aqueous solution of iron (II) sulfate heptahydrate; (ii) dipping of the iron-containing mesostructures in a solution of bipyridine ligands in acetonitrile. The in situ formation of the [Fe(bpy)3]2+ complex is evidenced by its characteristic optical absorption spectrum, and elemental composition analysis using X-ray photoelectron spectroscopy. The measured optical and electrochemical properties of immobilized [Fe(bpy)3]2+ complexes are not altered by confinement in the nanostructured silica thin film.

Multi-stimuli Photo and Redox-active Nanostructured Mesoporous Silica Films on Transparent Electrodes.

Silica matrices hosting transition metal guest complexes may offer remarkable platforms for the development of advanced functional devices. We report here the elaboration of ordered and vertically oriented mesoporous silica thin films containing covalently attached tris(bipyridine)iron derivatives using a combination of electrochemically assisted self-assembly (EASA) method and Huisgen cycloaddition reaction. Such a versatile approach is primarily used to bind nitrogen-based chelating ligands such as (4-[(2-propyn-1-yloxy)]4'-methyl-2,2'-bypiridine, bpy') inside the nanochannels. Further derivatization of the bpy'-functionalized silica thin films is then achieved via a subsequent in-situ complexation step to generate [Fe(bpy)2 (bpy')]2+ inside the mesopore channels. After giving spectroscopic evidences for the presence of such complexes in the functionalized film, electrochemistry is used to transform the confined diamagnetic (S=0) FeLSbpy2bpy'2+ species to paramagnetic (S=1/2) oxidized FeLSbpy2bpy'3+ species in a reversible way, while blue light irradiation (λ=470 nm) enables populating the short-lived paramagnetic (S=2) FeHSbpy2bpy'2+ excited state. [Fe(bpy)2 (bpy')]2+ -functionalized ordered films are therefore both electro- and photo-active through the manipulation of the oxidation state and spin state of the confined complexes, paving the way for their integration in optoelectronic devices.

Synthesis of Vertically Aligned Porous Silica Thin Films Functionalized by Silver Ions.

In this work, we have developed a chemical procedure enabling the preparation of highly ordered and vertically aligned mesoporous silica films containing selected contents of silver ions bonded inside the mesopore channels via anchoring propyl-carboxyl units. The procedure involves the electrochemically assisted self-assembly co-condensation of tetraethoxysilane and (3-cyanopropyl)triethoxysilane in the presence of cetyltrimethylammonium bromide as a surfactant, the subsequent hydrolysis of cyano groups into carboxylate ones, followed by their complexation with silver ions. The output materials have been electrochemically characterized with regard to the synthesis effectiveness in order to confirm and quantify the presence of the silver ions in the material. The mesostructure has been observed by transmission electron microscopy. We have pointed out that it is possible to finely tune the functionalization level by controlling the co-condensation procedure, notably the concentration of (3-cyanopropyl)triethoxysilane in the synthesis medium.

Discriminatory ability of anthropometric measurements of central fat distribution for prediction of post-prandial hyperglycaemia in patients with normal fasting glucose: the DICAMANO Study.

BACKGROUND AND AIMS: Obesity is associated with impaired glucose tolerance which is a risk factor for cardiovascular risk. However, the oral glucose tolerance test (OGTT) is not usually performed in patients with normal fasting glycaemia, thus offering false reassurance to patients with overweight or obesity who may have post-prandial hyperglycaemia. As an alternative to resource demanding OGTTs, we aimed to examine the predictive value of anthropometric measures of total and central fat distribution for post-prandial hyperglycaemia in patients with overweight and obesity with normal fasting glycaemia enrolled in the DICAMANO study. METHODS: We studied 447 subjects with overweight/obesity with a fasting glucose value ≤ 5.5 mmol l-1 (99 mg dl-1) and BMI ≥ 25 kg/m2 who underwent a 75-g OGTT. Post-prandial hyperglycaemia was defined as a glucose level ≥ 7.8 mmol l-1 (140 mg dl-1) 2-h after the OGTT. The anthropometric measurements included body mass index, body adiposity index, waist circumference, neck circumference, waist-to-hip ratio and waist-to-height ratio. RESULTS: The prevalence of post-prandial hyperglycaemia was 26%. Mean 1-h OGTT glucose levels, insulin resistance and beta cell dysfunction was higher in those subjects in the highest tertile for each anthropometric measurement, irrespective of fasting glucose level. Central fat depot anthropometric measurements were strongly and independently associated with an increased risk of post-prandial hyperglycaemia. After multivariable-adjustment for fasting plasma glucose level, smoking, and physical activity level, the odds ratio (95% confidence intervals) for the presence of post-prandial hyperglycaemia for neck circumference, waist circumference and waist-to-height ratio were 3.3 (1.4, 7.7), 2.4 (1.4, 4.4) and 2.5 (1.4, 4.5), respectively. CONCLUSIONS: In this large and comprehensively phenotyped cohort, one in four subjects had post-prandial hyperglycaemia despite normal fasting glycaemia. Anthropometric indices of central fat distribution were strongly and independently associated with an increased risk of post-prandial hyperglycaemia. These results support the association between central adiposity and glucose derangements and demonstrate the clinical usefulness of anthropometric measurements as screening tools for the selection of patients who are most likely to benefit from an OGTT. Trial registration ClinicalTrials.gov Identifier: NCT03506581. Registered 24 April 2018-Retrospectively registered, https://clinicaltrials.gov/ct2/show/NCT03506581.

Mesoporous Silica-Based Materials for Electronics-Oriented Applications.

Electronics, and nanoelectronics in particular, represent one of the most promising branches of technology. The search for novel and more efficient materials seems to be natural here. Thus far, silicon-based devices have been monopolizing this domain. Indeed, it is justified since it allows for significant miniaturization of electronic elements by their densification in integrated circuits. Nevertheless, silicon has some restrictions. Since this material is applied in the bulk form, the miniaturization limit seems to be already reached. Moreover, smaller silicon-based elements (mainly processors) need much more energy and generate significantly more heat than their larger counterparts. In our opinion, the future belongs to nanostructured materials where a proper structure is obtained by means of bottom-up nanotechnology. A great example of a material utilizing nanostructuring is mesoporous silica, which, due to its outstanding properties, can find numerous applications in electronic devices. This focused review is devoted to the application of porous silica-based materials in electronics. We guide the reader through the development and most crucial findings of porous silica from its first synthesis in 1992 to the present. The article describes constant struggle of researchers to find better solutions to supercapacitors, lower the k value or redox-active hybrids while maintaining robust mechanical properties. Finally, the last section refers to ultra-modern applications of silica such as molecular artificial neural networks or super-dense magnetic memory storage.

Vertically Aligned and Ordered One-Dimensional Mesoscale Polyaniline.

The growth of vertically aligned and ordered polyaniline nanofilaments is controlled by potentiostatic polymerization through hexagonally packed and oriented mesoporous silica films. In such small pore template (2 nm in diameter), quasi-single PANI chains are likely to be produced. From chronoamperometric experiments and using films of various thicknesses (100-200 nm) it is possible to evidence the electropolymerization transients, wherein each stage of polymerization (induction period, growth, and overgrowth of polyaniline on mesoporous silica films) is clearly identified. The advantageous effect of mesostructured silica thin films as hard templates for the generation of isolated polyaniline nanofilaments is demonstrated from enhancement of the reversibility between the conductive and the nonconductive states of polyaniline and the higher electroactive surface areas displayed for all mesoporous silica/PANI composites. The possibility to control and tailor the growth of conducting polymer nanofilaments offers numerous opportunities for applications in various fields including energy, sensors and biosensors, photovoltaics, nanophotonics, or nanoelectronics.

Electrografting of 3-Aminopropyltriethoxysilane on a Glassy Carbon Electrode for the Improved Adhesion of Vertically Oriented Mesoporous Silica Thin Films.

Vertically oriented mesoporous silica has proven to be of interest for applications in a variety of fields (e.g., electroanalysis, energy, and nanotechnology). Although glassy carbon is widely used as an electrode material, the adherence of silica deposits is rather poor, causing mechanical instability. A solution to improve the adhesion of mesoporous silica films onto glassy carbon electrodes without compromising the vertical orientation and the order of the mesopores will greatly contribute to the use of this kind of modified carbon electrode. We propose here the electrografting of 3-aminopropyltriethoxysilane on glassy carbon as a molecular glue to improve the mechanical stability of the silica film on the electrode surface without disturbing the vertical orientation and the order of the mesoporous silica obtained by electrochemically assisted self-assembly. These findings are supported by a series of surface chemistry techniques such as X-ray photoelectron spectroscopy, scanning and transmission electron microscopy, and cyclic voltammetry. Finally, methylviologen was used as a model redox probe to investigate the cathodic potential region of both glassy carbon and indium tin oxide electrodes modified with mesoporous silica in order to demonstrate further the interest in the approach developed here.

A multi-addressable switch based on the dimethyldihydropyrene photochrome with remarkable proton-triggered photo-opening efficiency.

A series of photochromic derivatives based on the trans-10b,10c-dimethyl-10b,10c-dihydropyrene (DHP, "closed form") skeleton has been synthesized and their photoisomerization leading to the corresponding cyclophanediene (CPD, "open form") isomers has been investigated by UV/Vis and (1) H NMR spectroscopies. Substitution of the DHP core with electron-withdrawing pyridinium groups was found to have major effects on the photoisomerization efficiency, the most remarkable examples being to enhance the quantum yield of the opening reaction and to allow fast and quantitative conversions at much lower radiant energies. This effect was rationalized by theoretical calculations. We also show that the reverse reaction, that is, going from the open form to the closed form, can be electrochemically triggered by oxidation of the CPD unit and that the photo-opening properties of pyridine-substituted DHPs can be efficiently tuned by protonation, the system behaving as a multi-addressable molecular switch. These multi-addressable photochromes show promise for the development of responsive materials.

183W INADEQUATE 2D NMR spectroscopy of hetero arsenato-phosphato-tungstate P(V)/As(V) substitution in Dawson-type α-[As(x)P(2-x)W18O62]6- (x = 0-2) and α-[H4As(y)P(1-y)W18O62]7- (y = 0, 1).

The Dawson-type arsenato-phosphato-tungstate α-[AsPW18O62](6-) has been prepared and unambiguously identified for the first time. A comparative study including the four other already known compounds, the symmetric α-[X2W18O62](6-) and unsymmetric α-[H4XW18O62](7-) for X = P(V), As(V), has been performed by spectroscopic (183)W and (31)P NMR. 2-D (183)W INADEQUATE experiments were systematically employed to unequivocally verify structures, assign all resonances, and determine precisely (2)JW-O-W scalar couplings. The effects of P/As substitutions, generating unsymmetric structures, on the NMR observables δW-183, δP-31, (2)JW-O-W, and (2)JW-O-P are discussed in relation to their bond length and bond angle alteration. General trends with respect to NMR parameter variations have been found when filling central cavities with P or As atoms, with less pronounced effects for As than for P. In addition, NMR characterization of three other isomers, i.e., ß-[X2W18O62](6-) and γ-[As2W18O62](6-), were also provided for comparison. The present NMR results could serve as representative reference data for understanding the relationship between structure and NMR observables in polyoxotungstates.

Electrochemically assisted generation of highly ordered azide-functionalized mesoporous silica for oriented hybrid films.

One key challenge in inorganic mesoporous films is the development of oriented mesostructures with vertical channels, and even more challenging is their functionalization while maintaining accessible the selected surface groups. Combining the electrochemically assisted deposition of ordered and oriented azide-functionalized mesoporous silica with alkyne-azide click chemistry enables such nanostructured and vertically aligned hybrid films to be obtained with significant amounts of active organic functional groups, as illustrated for ferrocene and pyridine functions. A good level of mesostructural order was obtained, namely up to 40% of organosilane in the starting sol. The method could be applied to a wide variety of functional groups, thus offering numerous new opportunities for applications in various fields.

Assessing the Influence of Confinement on the Stability of Polyoxometalate-Functionalized Surfaces: A Soft Sequential Immobilization Approach for Electrochromic Devices.

A functionalization process has been developed and the experimental conditions optimized allowing the immobilization of first-row transition metal (Mn+) containing polyoxometalates (POMs) with the formula [M(H2O)P2W17O61](10-n)- on transparent indium-tin oxide (ITO) electrodes for electrochromic applications. Both flat ITO grafted with 4-sulfophenyl moieties and sulfonate-functionalized vertically oriented silica films on ITO have been used as electrode supports to evaluate possible confinement effects provided by the mesoporous matrix on the stability of the modified surfaces and their electrochromic properties. Functionalization involved a two-step sequential process: (i) the immobilization of hexaaqua metallic ions, such as Fe(H2O)63+, onto the sulfonate-functionalized materials achieved through hydrogen bonding interactions between the sulfonate functions and aqua ligands (water molecules) coordinated to the metallic ions facilitating and stabilizing the attachment of the metallic ions to the sulfonated surfaces; (ii) their coordination to [P2W17O61]10- species to generate "in situ" the target [Fe(H2O)P2W17O61]7- moieties. Comparison of the characterized surfaces clearly evidenced a significant improvement in the long-term stability of the nanostructured [Fe(H2O)P2W17O61]7--functionalized silica films compared to the less constrained flat [Fe(H2O)P2W17O61]7--modified ITO electrodes for which a rapid loss of [P2W17O61]10- species was observed. Concordantly, the [Fe(H2O)P2W17O61]7- POM confined in the mesoporous films coated on ITO gave rise to much better and stable electrochromic properties, with a transmittance modulation of 40% at 515 nm.

Proton-triggered chemoselective halogenation of aliphatic C-H bonds with nonheme FeIV-oxo complexes.

Halogenation of aliphatic C-H bonds is a chemical transformation performed in nature by mononuclear nonheme iron dependent halogenases. The mechanism involves the formation of an iron(IV)-oxo-chloride species that abstracts the hydrogen atom from the reactive C-H bond to form a carbon-centered radical that selectively reacts with the bound chloride ligand, a process commonly referred to as halide rebound. The factors that determine the halide rebound, as opposed to the reaction with the incipient hydroxide ligand, are not clearly understood and examples of well-defined iron(IV)-oxo-halide compounds competent in C-H halogenation are scarce. In this work we have studied the reactivity of three well-defined iron(IV)-oxo complexes containing variants of the tetradentate 1-(2-pyridylmethyl)-1,4,7-triazacyclononane ligand (Pytacn). Interestingly, these compounds exhibit a change in their chemoselectivity towards the functionalization of C-H bonds under certain conditions: their reaction towards C-H bonds in the presence of a halide anionleads to exclusive oxygenation, while the addition of a superacid results in halogenation. Almost quantitative halogenation of ethylbenzene is observed when using the two systems with more sterically congested ligands and even the chlorination of strong C-H bonds such as those of cyclohexane is performed when a methyl group is present in the sixth position of the pyridine ring of the ligand. Mechanistic studies suggest that both reactions, oxygenation and halogenation, proceed through a common rate determining hydrogen atom transfer step and the presence of the acid dictates the fate of the resulting alkyl radical towards preferential halogenation over oxygenation.

A multicolor photoinitiator for cationic polymerization and interpenetrated polymer network synthesis: 2,7-di-tert-butyldimethyldihydropyrene.

For polymer synthesis upon visible light, actual photoinitiator operates in a restricted part of the spectrum. As a consequence, several photoinitiators are necessary to harvest all of the emitted visible photons. Herein, 2,7-di-tert-butyldimethyldihydropyrene is used for the first time as a multicolor photoinitiator for the cationic polymerization of epoxides. Upon addition of diphenyliodonium hexafluorophosphate and optionally N-vinylcarbazole, the originality of this approach is to allow efficient monomer conversions under various excitation light sources in the 360-650 nm wavelength range: halogen lamps, and light-emitting and laser diodes. The synthesis of an interpenetrated polymer network from an epoxide/acrylate blend using a red light at 635 nm is also feasible. The formed polymer material exhibits a photochromic character.

Electrochemical behavior of α1/α2-[Fe(H2O)P2W17O61](7-) isomers in solution: experimental and DFT studies.

The unusual redox behavior displayed by the two isomers of the Wells-Dawson phosphotungstate anion [Fe(H(2)O)P(2)W(17)O(61)](7-) is presented. The electrochemical measurements have been performed in aqueous media at different pH values from 0.5 up to 8.0. The cyclic voltammetry has also been carried out in organic media to get additional experimental data to establish the effect of the protonation on the redox properties of both isomers. At high pH values (pH ≥ 6) or in an organic medium, the reduction of the Fe center is easier in the case of the alpha-1 isomer, whereas for the alpha-2 isomer such reduction takes place at more negative potentials, as expected. In contrast, at lower pH values (pH ≤ 5), an inversion of this trend is observed, and the reduction of the Fe center becomes easier for the alpha-2 isomer compared to the alpha-1. We were able to highlight the influence of the pH and the pK(a) of the electrolyte on POM-based redox potentials given the pK(a) of the latter. A complementary theoretical study has also been performed to explain the experimental data obtained. In this sense, the results obtained from the DFT study are in good agreement with the experimental data mentioned above and have provided additional information for the electrochemical behavior of both isomers according to their different molecular orbital energies. We have also shown the influence of protonation state of the iron derivative on the relative reduction potentials of both isomers.

Polyoxometalates functionalized by bisphosphonate ligands: synthesis, structural, magnetic, and spectroscopic characterizations and activity on tumor cell lines.

We report the synthesis and characterization of eight new Mo, W, or V-containing polyoxometalate (POM) bisphosphonate complexes with metal nuclearities ranging from 1 to 6. The compounds were synthesized in water by treating Mo(VI), W(VI), V(IV), or V(V) precursors with biologically active bisphosphonates H(2)O(3)PC(R)(OH)PO(3)H(2) (R = C(3)H(6)NH(2), Ale; R = CH(2)S(CH(3))(2), Sul and R = C(4)H(5)N(2), Zol, where Ale = alendronate, Sul = (2-Hydroxy-2,2-bis-phosphono-ethyl)-dimethyl-sulfonium and Zol = zoledronate). Mo(6)(Sul)(2) and Mo(6)(Zol)(2) contain two trinuclear Mo(VI) cores which can rotate around a central oxo group while Mo(Ale)(2) and W(Ale)(2) are mononuclear species. In V(5)(Ale)(2) and V(5)(Zol)(2) a central V(IV) ion is surrounded by two V(V) dimers bound to bisphosphonate ligands. V(6)(Ale)(4) can be viewed as the condensation of one V(5)(Ale)(2) with one additional V(IV) ion and two Ale ligands, while V(3)(Zol)(3) is a triangular V(IV) POM. These new POM bisphosphonates complexes were all characterized by single-crystal X-ray diffraction. The stability of the Mo and W POMs was studied by (31)P NMR spectroscopy and showed that all compounds except the mononuclear Mo(Ale)(2) and W(Ale)(2) were stable in solution. EPR measurements performed on the vanadium derivatives confirmed the oxidation state of the V ions and evidenced their stability in aqueous solution. Electrochemical studies on V(5)(Ale)(2) and V(5)(Zol)(2) showed reduction of V(V) to V(IV), and magnetic susceptibility investigations on V(3)(Zol)(3) enabled a detailed analysis of the magnetic interactions. The presence of zoledronate or vanadium correlated with the most potent activity (IC(50)~1-5 µM) against three human tumor cell lines.

Effects and mechanisms of mindfulness training and physical exercise on cognition, emotional wellbeing, and brain outcomes in chronic stroke patients: Study protocol of the MindFit project randomized controlled trial.

Background: Post-stroke cognitive and emotional complications are frequent in the chronic stages of stroke and have important implications for the functionality and quality of life of those affected and their caregivers. Strategies such as mindfulness meditation, physical exercise (PE), or computerized cognitive training (CCT) may benefit stroke patients by impacting neuroplasticity and brain health. Materials and methods: One hundred and forty-one chronic stroke patients are randomly allocated to receive mindfulness-based stress reduction + CCT (n = 47), multicomponent PE program + CCT (n = 47), or CCT alone (n = 47). Interventions consist of 12-week home-based programs five days per week. Before and after the interventions, we collect data from cognitive, psychological, and physical tests, blood and stool samples, and structural and functional brain scans. Results: The effects of the interventions on cognitive and emotional outcomes will be described in intention-to-treat and per-protocol analyses. We will also explore potential mediators and moderators, such as genetic, molecular, brain, demographic, and clinical factors in our per-protocol sample. Discussion: The MindFit Project is a randomized clinical trial that aims to assess the impact of mindfulness and PE combined with CCT on chronic stroke patients' cognitive and emotional wellbeing. Furthermore, our design takes a multimodal biopsychosocial approach that will generate new knowledge at multiple levels of evidence, from molecular bases to behavioral changes. Clinical trial registration: www.ClinicalTrials.gov, identifier NCT04759950.

Photochromic and redox properties of bisterpyridine ruthenium complexes based on dimethyldihydropyrene units as bridging ligands.

We report herein the synthesis and characterization of four new bisterpyridine dinuclear ruthenium complexes containing the dimethyldihydropyrene (DHP) photochrome as bridging ligand. A synthetic strategy has been developed based on a Suzuki coupling reaction to synthesize these novel terpyridine-DHPs. The reactivity of these different ligands and dinuclear ruthenium complexes with light was examined by (1)H NMR and monitoring the changes in their absorption spectra upon irradiation at controlled wavelengths. The free ligands and their corresponding ruthenium complexes all displayed photochromic properties with highly efficient conversion between the closed stable isomers (DHP) and their open forms (CPD). The properties of the compounds in their closed and open forms were investigated by cyclic voltammetry, spectroscopy, and luminescence measurements.