Photoswitchable optoelectronic properties of 2D MoSe2/diarylethene hybrid structures.

The ability to modulate optical and electrical properties of two-dimensional (2D) semiconductors has sparked considerable interest in transition metal dichalcogenides (TMDs). Herein, we introduce a facile strategy for modulating optoelectronic properties of monolayer MoSe2 with external light. Photochromic diarylethene (DAE) molecules formed a 2-nm-thick uniform layer on MoSe2, switching between its closed- and open-form isomers under UV and visible irradiation, respectively. We have discovered that the closed DAE conformation under UV has its lowest unoccupied molecular orbital energy level lower than the conduction band minimum of MoSe2, which facilitates photoinduced charge separation at the hybrid interface and quenches photoluminescence (PL) from monolayer flakes. In contrast, open isomers under visible light prevent photoexcited electron transfer from MoSe2 to DAE, thus retaining PL emission properties. Alternating UV and visible light repeatedly show a dynamic modulation of optoelectronic signatures of MoSe2. Conductive atomic force microscopy and Kelvin probe force microscopy also reveal an increase in conductivity and work function of MoSe2/DAE with photoswitched closed-form DAE. These results may open new opportunities for designing new phototransistors and other 2D optoelectronic devices.

Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based "N2O2" Complexes as Efficient NIR-Fluorophores.

Aza-boron-dipyrromethenes (Aza-BODIPYs) are an increasingly studied class of fluorophores. They can be seen as an azadipyrromethene ("aza-DIPY") ligand rigidified by a metalloid, a boron atom. Based on this idea, a series of complexes of group 13 metals (aluminum and gallium) have been synthesized and characterized. The impact of the metal and of the nature of the substituents of aza-DIPY core were investigated. The photophysical and electrochemical properties were determined, and an X-ray structure of an azaGaDIPY was obtained. These data reveal that azaGaDIPY and azaAlDIPY exhibit significant red-shifted fluorescence compared to their analogue aza-BODIPY. Their emission can go up to 800 nm for the maximum emission length and up to NIR-II for the emission tail. This, associated with their electrochemical stability (no metal release whether oxidized or reduced) makes them a promising class of fluorophores for optical medical imaging. Moreover, X-ray structure and molecular modeling studies have shown that this redshift seems to be more due to the geometry around the boron/metal than to the nature of the metal.

Assembly of Aggregation-Induced Emission Active Bola-Amphiphilic Macromolecules into Luminescent Nanoparticles Optimized for Two-Photon Microscopy In Vivo.

The (Z) and (E)-isomers of an extended tetraphenylethylene-based chromophore with optimized two-photon-induced luminescence properties are separated and functionalized with water-solubilizing pendant polymer groups, promoting their self-assembly in physiological media in the form of small, colloidal stable organic nanoparticles. The two resulting fluorescent suspensions are then evaluated as potential two-photon luminescent contrast agents for intravital epifluorescence and two-photon fluorescence microscopy. Comparisons with previously reported works involving similar fluorophores devoid of polymer side chains illustrate the benefits of later functionalization regarding the control of the self-assembly of the nano-objects and ultimately their biocompatibility toward the imaged organism.

O-Acetylated sugars in the gas phase: stability, migration, positional isomers and conformation.

O-Acetylations are functional modifications which can be found on different hydroxyl groups of glycans and which contribute to the fine tuning of their biological activity. Localizing the acetyl modifications is notoriously challenging in glycoanalysis, in particular because of their mobility: loss or migration of the acetyl group may occur through the analytical workflow. Whereas migration conditions in the condensed phase have been rationalized, little is known about the suitability of Mass Spectrometry to retain and resolve the structure of O-acetylated glycan isomers. Here we used the resolving power of infrared ion spectroscopy in combination with ab initio calculations to assess the structure of O-acetylated monosaccharide ions in the gaseous environment of a mass analyzer. N-Acetyl glucosamines were synthetized with an O-acetyl group in positions 3 or 6, respectively. The protonated ions produced by electrospray ionization were observed by mass spectrometry and their vibrational fingerprints were recorded in the 3 µm range by IRMPD spectroscopy (InfraRed Multiple Photon Dissociation). Experimentally, the isomers show distinctive IR fingerprints. Additionally, ab initio calculations confirm the position of the O-acetylation and resolve their gas phase conformation. These findings demonstrate that the position of O-acetyl groups is retained through the transfer from solution to the gas phase, and can be identified by IRMPD spectroscopy.

Metal-Free Visible-Light Synthesis of Arylsulfonyl Fluorides: Scope and Mechanism.

The first metal-free procedure for the synthesis of arylsulfonyl fluorides is reported. Under organo-photoredox conditions, aryl diazonium salts react with a readily available SO2 source (DABSO) to afford the desired product through simple nucleophilic fluorination. The reaction tolerates the presence of both electron-rich and -poor aryls and demonstrated a broad functional group tolerance. To shed the light on the reaction mechanism, several experimental techniques were combined, including fluorescence, NMR, and EPR spectroscopy as well as DFT calculations.

Reevaluating the Solution Photophysics of Tetraphenylethylene at the Origin of their Aggregation-Induced Emission Properties.

Although tetraphenylethylene (TPE) and its derivatives have been the most commonly used building blocks in the construction of molecules with aggregation-induced emission (AIE) properties, no absolute consensus exists regarding the mechanisms at the origin of the phenomenon. Restriction of intramolecular rotations (RIR) of peripheral phenyls has historically been a dominant paradigm, which has served as a valuable guideline in the molecular engineering of AIEgens. Yet, an increasing number of recent works have established that photoisomerization or photocyclization may actively participate in the nonradiative dissipation of the excitation energy. In this paper, the first experimental evaluation of the quantum efficiencies of these different processes is reported, and photoisomerization is shown to be by far the dominant photophysical pathway in solution, accounting for virtually all nonradiative decay of the molecule's excited state in degassed solution.

Determination of Photoinduced Radical Generation Quantum Efficiencies by Combining Chemical Actinometry and 19F NMR Spectroscopy.

We introduce a general and relatively straightforward protocol aimed at determining the absolute photoinduced radical generation efficiency via NMR monitoring. This approach relies on the use of a radical scavenger probe that combines a nitroxide moiety that specifically reacts with radicals and a trifluoromethyl group used as a 19F NMR signaling unit. Using an LED source, whose fluence is precisely determined by a chemical actinometry procedure also described herein, the method is used to determine the radical photogeneration quantum yields of three well-known polymerization initiators: azobisisobutyronitrile (AIBN), 4,4'-bis(N,N-diethylamino)benzophenone (BDEBP, a derivative of Michler's ethyl ketone), and 2,4,6-trimethylbenzoyl diphenylphosphine oxide (MAPO). The overall good agreement with values previously reported in the literature proves the robustness of this new method. We then extended the study to the precise measurement of the quantum yield of free-radical photogeneration on a newly synthesized photoinitiator used for two-photon direct laser writing. This study highlights the potential of this methodology for the quantitative determination of photoinduced radical generation efficiency used in many fields of applications.

Two-Photon Absorbing AIEgens: Influence of Stereoconfiguration on Their Crystallinity and Spectroscopic Properties and Applications in Bioimaging.

This paper aims at designing chromophores with efficient aggregation-induced emission (AIE) properties for two-photon fluorescence microscopy (2PFM), which is one of the best-suited types of microscopy for the imaging of living organisms or thick biological tissues. Tetraphenylethylene (TPE) derivatives are common building blocks in the design of chromophores with efficient AIE properties. Therefore, in this study, extended TPE AIEgens specifically optimized for two-photon absorption (2PA) are synthesized and the resulting (E/Z) isomers are separated using chromatography on chiral supports. Comparative characterization of the AIE properties is performed on the pure (Z) and (E) isomers and the mixture, allowing us, in combination with powder X-ray diffraction and solid-state NMR, to document a profound impact of crystallinity on solid-state fluorescence properties. In particular, we show that stereopure AIEgens form aggregates of superior crystallinity, which in turn exhibit a higher fluorescence quantum yield compared to diastereoisomers mixtures. Preparation of stereopure organic nanoparticles affords very bright fluorescent contrast agents, which are then used for cellular and intravital two-photon microscopy on human breast cancer cells and on zebrafish embryos.

O trabalho com os pais – da função deresíduo à surpresa

O lugar do sintoma da criança na família é a questão central desse texto que parte das principais referências teóricas de Lacan, para abordar que ensinamentos podemos apreender na prática em instituição. Um caso de um sujeito adolescente ilustra a importância do trabalho com os pais, as invenções do analista e a solução escolhida por este sujeito autista para lidar com o real em jogo(AU)

The perceived exertion to regulate a training program in young women.

The aim of this study was to compare the heart rate (HR) and the perceived exertion (PE) regulation of a training program in women and their effects on the cardiorespiratory responses. Twenty-seven women (mean age 22.4 ± 2.7 years) were randomly assigned to a control group (CG, n = 9), a heart rate group (HRG, n = 9), or a perceptive group (PG, n = 9). All subjects performed a maximal graded test (MGT) on a cycle ergometer before and after 6 weeks. The HR, V(O2)peak, maximal tolerated power (MTP), and PE were recorded during both MGTs. A 6-week interval training program was performed by both the HRG and PG. HR targets were used for the HRG and PE for the PG to readjust the power output. The results show that the V(O2)peak and the MTP increased significantly (p < 0.05) for both training groups, whereas the CG obtained no changes. As a consequence, PE could be a valuable tool to readjust the training load during an interval training program.

Can shoulder muscle coordination during the support scale at ring height be replicated during training exercises in gymnastics?

The support scale at ring height, the swallow, is a difficult strength element, usually performed in gymnastics. Coaches try to simulate the swallow position during training to strengthen muscles, specifically in the position used for competition. However, the real effect of this position's simulation on muscle force and coordination and consequently on the muscle activity has not been determined. The purpose of the study was to compare muscle activity and coordination during a swallow performed on the rings, using a counterweight and during 2 training exercises using dumbbells or barbells, respectively. Six top-level gymnasts participated in the study. Electromyograms from the biceps brachii, triceps brachii, deltoideus (clavicular part), pectoralis major, serratus anterior, infraspinatus, trapezius (middle part), and latissimus dorsi in the right shoulder were collected during the 4 exercises and analyzed using root mean square (RMS) and mean power frequency (MPF). The RMS were normalized to the maximal voluntary contraction, and a co-activation index was also determined between biceps and triceps brachii. Our results show specific shoulder muscle coordination for each exercise. As compared with the swallow on the rings, the pectoralis major participates less in shoulder flexion during the counterweight exercise, whereas the deltoideus is more activated during the dumbbells exercise (p < 0.05). The barbell exercise reduces the participation of the serratus anterior in stabilizing the scapula (p < 0.05). Training exercises must therefore be chosen with knowledge of the specific muscle coordination induced by each. The counterweight exercise preserves the pectoralis major. The barbell exercise reduces participation of the serratus anterior. The dumbbells exercise may be useful to prepare the rotator cuff muscles carefully for use.

Determination of the ventilatory threshold with affective valence and perceived exertion in trained cyclists: a preliminary study.

The aim of the present study was to determine if trained cyclists have perceptual markers that can be used to identify the ventilatory threshold during a maximal exercise test. Ten trained cyclists (age 25.20 +/- 4.94 years; VO2max 63.6 +/- 6.3 mL x min(-1) x kg(-1)) performed a maximal graded test on a cycling ergometer. Perceived exertion and affective valence were measured each min of the maximal graded test. The results indicate that ventilatory threshold, perceived exertion, and affective valence are significantly different compared to the values assessed 1 minute after ventilatory threshold. Moreover, there were a significant relationships between power output and perceived exertion (p < 0.01; r = 0.97) and affective valence (p < 0.01; r = 0.94) measured during the maximal graded test. These results confirm that at ventilatory threshold a lot of significant changes of perceptual parameters appear and may be good indicators for athletes to determine their ventilatory threshold during a training session. This method could be interesting for cyclists to control the exercise intensity during individual time trial.

Cardiovascular autonomic control during short-term thermoneutral and cool head-out immersion.

BACKGROUND: Moderately cold head-out water immersion stimulates both baro- and cold-receptors, and triggers complex and contradictory effects on the cardiovascular system and its autonomic nervous control. OBJECTIVES: To assess the effects of water immersion and cold on cardiovascular status and related autonomic nervous activity. METHODS: Hemodynamic variables and indexes of autonomic nervous activity (analysis of heart rate and blood pressure variability) were evaluated in 12 healthy subjects during 3 exposures of 20 min each in the upright position, i.e., in air (AIR, 24-25 degrees C), and during head-out water immersion at 35-36 degrees C (WIn) and 26-27 degrees C (WIc). RESULTS: Plasma noradrenaline, systolic and diastolic blood pressure, and total peripheral resistances were reduced during WIn compared to AIR (263.9 +/- 39.4 vs. 492.5 +/- 35.7 pg x ml(-1), 116.5 +/- 3.7 and 65.4 +/- 1.7 mmHg vs. 140.8 +/- 4.7 and 89.8 +/- 2.8 mmHg, 14.1 +/- 1.0 vs. 16.3 +/- 0.9 mmHg x L(-1) x min, respectively) while they were increased during WIc (530.8 +/- 84.7 pg ml(-1), 148.0 +/- 7.0 mmHg, 80.8 +/- 3.0 mmHg, and 25.8 +/- 1.9 mmHg x L(-1) x min, respectively). The blood pressure variability was reduced to the same extent during WIc and Win compared to AIR. Heart rate decreased during WIn (67.8 +/- 2.7 vs. 81.2 +/- 2.7 bpm during AIR), in parallel with an increased cardiac parasympathetic activity. This pattern was strengthened during WIc (55.3 +/- 2.2 bpm). CONCLUSIONS: Thermoneutral WI lowered sympathetic activity and arterial tone, while moderate whole-body skin cooling triggered vascular sympathetic activation. Conversely, both WI and cold triggered cardiac parasympathetic activation, highlighting a complex autonomic control of the cardiovascular system.

Conditions of autonomic reciprocal interplay versus autonomic co-activation: effects on non-linear heart rate dynamics.

The present study was aimed at investigating the autonomic nervous system influences on the fractal organization of human heart rate during sympathovagal interactions, with special emphasize on the short-term fractal organization in heart rate variability (HRV), as assessed by the scaling exponent (alpha(1)) of the detrended fluctuation analysis. Linear and non-linear HRV analyses were used to study the sympathetic and vagal modulation of heart rate in ten healthy men (mean +/- SEM; age 26 +/- 1 years) during conditions of 1) increased sympathetic activity and vagal withdrawal (head-up tilt), 2) decreased sympathetic activity and increased vagal outflow (thermoneutral upright head-out water immersion, WIn), and 3) simultaneous activation of the two arms of the autonomic nervous activity (upright head-out immersion in cold water, WIc). Hemodynamic and linear HRV results were consistent with previous reports during similar physiological conditions. alpha(1) increased significantly during head-up tilt (from 0.71 +/- 0.13 supine to 0.90 +/- 0.15 upright) and WIn (0.86 +/- 0.10) and was significantly decreased during WIc (0.61 +/- 0.15). Thus, alpha(1) increased when the cardiac autonomic interplay was altered in a reciprocal fashion, whatever the direction of the balance change. Conversely, alpha(1) decreased during the concomitant activation of both vagal and sympathetic activities. The results of linear analysis were necessary to precisely define the direction of change in autonomic control revealed by an increase in alpha(1), while the direction of change in alpha(1) indicated whether an increased vagal activity is coupled with a decreased or increased sympathetic activation. Using both linear and non-linear analysis of HRV may increase the understanding of changes in cardiac autonomic status.

Neuro-mechanical and chemical influences on locomotor respiratory coupling in humans.

Mechanisms of coordination between breathing and movement during dynamic exercise are still a matter of debate. This study aimed to examine the degree of coordination between breathing and arm propulsion patterns and to compare the relative contribution of neuro-mechanical and chemical factors. Thirteen trained cross-country skiers performed constant submaximal 6-min roller skiing exercises on a motorized driven treadmill in two different poling techniques (V2A and V2 skating techniques) at two exercise intensity levels corresponding to the first and second ventilatory thresholds. The timing of arm propulsion movements in V2A and V2 techniques was considered as a mechanical/neural influence on breathing whereas exercise intensity represented the metabolic demand to breathing. The degree of coordination, expressed as the percentage of breaths presenting a constant phase interval (time between an arbitrarily chosen point of the arm movement cycle and the onset of expiration) was significantly higher in V2A than V2 (P<0.05) while exercise intensity had no effect on the degree of coordination. We concluded that locomotor-respiratory coupling occurs in cross-country skiing as simulated by roller skiing because of strong influences from neuro-mechanical factors.

Paced breathing in roller-ski skating: effects on metabolic rate and poling forces.

PURPOSE: This study aimed (1) to determine whether paced breathing (synchronization of the expiration phase with poling time) would reduce the metabolic rate and dictate a lower rate of perceived exertion (RPE) than does spontaneous breathing and (2) to analyze the effects of paced breathing on poling forces and stride-mechanics organization during roller-ski skating exercises. METHODS: Thirteen well-trained cross-country skiers performed 8 submaximal roller-skiing exercises on a motorized driven treadmill with 4 modes of skiing (2 skating techniques, V2 and V2A, at 2 exercise intensities) by using 2 patterns of breathing (unconscious vs conscious). Poling forces and stride-mechanics organization were measured with a transducer mounted in ski poles. Oxygen uptake (VO2) was continuously collected. After each bout of exercise RPE was assessed by the subject. RESULTS: No difference was observed for VO2 between spontaneous and paced breathing conditions, although RPE was lower with paced breathing (P < .05). Upper-limb cycle time and recovery time were significantly (P < .05) increased by paced breathing during V2A regardless of the exercise intensity, but no changes for poling time were observed. A slight trend of increased peak force with paced breathing was observed (P = .055). CONCLUSION: The lack of a marked effect of paced breathing on VO2 and some biomechanical variables could be explained by the extensive experience of our subjects in cross-country skiing.

No influence of hypoxia on coordination between respiratory and locomotor rhythms during rowing at moderate intensity.

Besides neuro-mechanical constraints, chemical or metabolic stimuli have also been proposed to interfere with the coordination between respiratory and locomotor rhythms. In the light of the conflicting data observed in the literature, this study aimed to assess whether acute hypoxia modifies the degree of coordination between respiratory and locomotor rhythms during rowing exercises in order to investigate competitive interactions between neuro-mechanical (movement) and chemical (hypoxia) respiratory drives. Nine male healthy subjects performed one submaximal 6-min rowing exercise on a rowing ergometer in both normoxia (altitude: 304 m) and acute hypoxia (altitude: 2877 m). The exercise intensity was about 40 % and 35 % (for normoxia and hypoxia conditions, respectively) of the individual maximal power output measured during an incremental rowing test to volitional exhaustion carried out in normoxia. Metabolic rate and minute ventilation were continuously collected throughout exercise. Locomotor movement and breathing rhythms were continuously recorded and synchronized cycle-by-cycle. The degree of coordination was expressed as a percentage of breaths starting during the same phase of the locomotor cycle. For a same and a constant metabolic rate, acute hypoxia did not influence significantly the degree of coordination (mean ± SEM, normoxia: 20.0 ± 6.2 %, hypoxia: 21.3 ± 11.1 %, p > 0.05) while ventilation and breathing frequency were significantly greater in hypoxia. Our results may suggest that during rowing exercise at a moderate metabolic load, neuro-mechanical locomotion-linked respiratory stimuli appear "stronger "than peripheral chemoreceptors- linked respiratory stimuli induced by hypoxia, in the context of our study. Key pointsChanges in breathing frequency and ventilation induced by altitude have no effect on the degree of coordination between locomotor and breathing rhythms during moderate rowing exercise.During moderate rowing exercise in hypoxia, the neuro-mechanical drives still dominate over chemoreceptive stimuli.These above statements have to be taken carefully because it might be quite different during activities where the coupling between locomotor and breathing rhythms is less constrained (e.g., running, cycling).

Influence of a 6-week arm exercise program on walking ability and health status after hip arthroplasty: a 1-year follow-up pilot study.

The influence of an upper-limb interval-training program after total hip arthroplasty (THA) in elderly patients was studied during a 1 yr follow-up on health status and walking ability. After surgery, 14 patients were randomly assigned to the control group that started a 6 wk general rehabilitation program or the training group that combined it with an interval exercise program on an arm ergometer. A Western Ontario and McMaster Universities (WOMAC) Osteoarthritis Index was completed 1 mo before and 2 mo and 1 yr after surgery. A 6 min walking test was performed at 2 mo and 1 yr after surgery. The training group covered a significantly longer distance than the control group in the 6 min walk test and obtained significantly lower WOMAC scores both at 2 mo and 1 yr after surgery. However, both groups significantly improved in WOMAC and in their performance during the survey. Endurance-type upper-body aerobic training in a rehabilitation program might be important after THA.

Effects of two devices on the surface electromyography responses of eleven shoulder muscles during Azarian in gymnastics.

Difficult elements of strength such as Azarian must be presented on the rings. Specific-muscles training may be realized with 2 devices, the Herdos and the Belt, both of which reproduce the competitive situation and allow many repetitions. The purpose of this study was therefore to compare the shoulder muscle activity during the performance of Azarian with each device. Our results show that muscles rhomboid, supraspinatus, deltoid (anterior, middle, and posterior parts), biceps brachii, and triceps brachii have significant (p < 0.05) higher root mean square value when gymnasts use the Belt compared with the Herdos. Although the Herdos and the Belt reproduce competitive movement, their muscle activities are quite different. The Herdos reduces the stress on the shoulder and elbow joints, whereas the Belt induces higher muscle activity and probably provides closer muscle synergisms to the rings.

Effects of steady-state exercise on perceived pain: comparison of sedentary students and cyclists.

In this study, the effect of fitness level on perceived pain before and after a steady state exercise was investigated. Ten trained cyclists (M age=25.2 yr., SD=4.9) and 10 sedentary men (Mage=24.5 yr., SD=2.2) performed a maximal graded test on a cycle ergometer. At least 48 hr. later the participants of both groups performed a 30-min. steady-state cycling test at 75% of VO2 max. Before the steady-state exercise and 5- and 30-min. postexercise, a pressure pain stimulation test was applied on the finger of each participant. Perceived pain was measured with Borg's CR10 scale at the end of each pain stimulation. The results indicated no significant changes in perceived pain between the pre-exercise and 5- and 30-min. postexercise values (effect sizes=.07 and .19, respectively). Moreover, no significant difference in perceived pain was found between the groups for pre-exercise (ES=.02) and 5- and 30-min. postexercise (ES=.16 and .21, respectively) values. These results do not confirm the analgesic effects usually observed after steady state exercise. Therefore, it is not possible to compare the analgesic effect of this exercise mode between participants characterized by different fitness levels.