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INTRODUCTION: Endoscopic ultrasound-guided gastroenterostomy (EUS-GE) is increasingly used in the setting of malignant gastric outlet obstruction (GOO). However, little is known about the role of primary EUS-GE. The aim of the present study is to compare the outcomes of EUS-GE by using the freehand technique as a first- and second-line approach after enteral stenting (ES). METHODS: This is an observational single-center study using a prospectively collected database. All consecutive patients who underwent an EUS-GE using the freehand technique due to malignant GOO were included. Patients with previous gastric surgery, a wire-guided EUS-GE technique, or those presenting without GOO were excluded. The primary outcome was the clinical success, defined as a solid oral intake at 1 week after the procedure (GOO Score, GOOSS ≥ 2). The secondary outcomes were technical success and adverse event (AE) rates. The impact on nutritional parameters was also assessed. RESULTS: Forty-five patients underwent an EUS-GE for all indications. Finally, 28 patients (mean age: 63 ± 17.2 years, 57.1% male) with (n = 13, 46.4%) and without (n = 15, 53.6%) a previous ES were included. The technical success was achieved in 25 cases (89.3%), with no differences between the two groups (92.3% vs. 86.7%, p = 1). The median limb diameter and procedure time were 27 mm (range:15-48) and 37 min. Overall, clinical success was achieved in 22 cases (88%), with three failures due to AEs (n = 2) or peritoneal carcinomatosis (n = 1). The diet progression was quicker in patients with a previous ES (GOOSS at 48 h, 2 vs. 1, p = 0.023), but the GOOSS at 1 week (p = 0.299), albumin gain (p = 0.366), and BMI gain (0.257) were comparable in the two groups. The AE rate was 7.1%. CONCLUSIONS: EUS-GE achieves a high technical and clinical success in patients with GOO regardless of the presence of a previous ES. Patients with previous ES may have a quicker progression of their diet, but the GOOSS and nutritional status in the long term at 1 week or 1 month are comparable. Primary EUS-GE might require fewer procedures and less discontinuation of chemotherapy to achieve a comparable result. ispartof: CANCERS vol:14 issue:22 ispartof: location:Switzerland status: published

The wind resource offshore is often excellent due to a higher average wind speed and lower turbulence intensity. Jacket structures are the most common offshore platforms for extraction of oil and natural gas in relative low water depths. When the offshore resources run out, these structures must be displaced to another area containing underground resources or removed in the case of reaching their design life. Therefore, one possible procedure to reduce the carbon footprint on the planet, allowing society to rely on promising sources of ’clean’ energy while salvaging these oil and gas platforms, is to consider the transformation of these oil and gas platforms into offshore wind turbine support structures. The present research focus on the possibility of converting such structures for gas extraction into offshore platforms for wind turbines. In this study, a comparison between the behavior of horizontal and vertical axis wind turbines on the same offshore platform is presented. In this comparison, two different software programs are used: MATLAB and SAP2000. The model proposed is a new simplified tool used to study the structural analysis of the jacket structures, developed and summarized in 10 steps, adopted to evaluate the behavior of the platform with the wind tower configurations.

Fatigue damage is treacherous and can lead to the failure of offshore structures. The purpose of this research is to evaluate and discuss the stress concentration factor (SCF) values for tw...

Sclerosing Angiomatoid Nodular Transformation (SANT) is a rare and benign lesion arising from the red pulp of the spleen, with an unknown etiopathogenesis. These tumors are usually asymptomatic and are found incidentally on radiographic examination. Therefore, high clinical suspicion is of great importance for the diagnosis. Splenectomy provides complete cure, and no recurrence and/or malignant transformation was reported to date. In this study, a rare case of SANT was reported in aadolescent male, and was discussed with the relevant literature.

Molecular switches are chemical compounds exhibiting the possibility of reversible transformations between their different forms accompanied by a modification in their properties. Among these, switching of multi-addressable Benzazolo-OXazolidines (BOXs) from a closed form to an open form results in drastic modifications in their linear and nonlinear optical properties. Here, we target molecules containing two identical BOX units (DiBOX) connected by different π-conjugated linkers, and we combine synthesis, UV/visible absorption, and hyper-Rayleigh scattering (HRS) measurements, together with density functional theory (DFT) calculations. Three derivatives have been considered, which differ by the linker: (i) a bithiophene moiety (Bt), (ii) two 3,4-ethylenedioxythiopene (EDOT) units, and (iii) a triad composed of an EDOT-thiophene-EDOT sequence (TtO). As a matter of fact, these systems can adopt three states (CF-CF, POF-POF, and CF-POF) depending on the closed form (CF) or the protonated open form (POF) of each BOX unit. Despite chemical equivalence, stepwise switching of such systems under the addition of a chemical acid or an oxidant has been experimentally evidenced for two of them (DiBOX-Bt and DiBOX-TtO). Then, DFT calculations show that the first BOX opening leads to the formation of a push-pull π-conjugated segment, exhibiting a huge increase in the first hyperpolarizability (β) and a bathochromic shift with respect to the fully closed form. On the contrary, the second BOX opening induces not only a slight bathochromic shift but also a reduction in their β values conferring the great and uncommon abilities to modulate their linear and nonlinear properties over three discrete levels. Among these results, those on DiBOX-Bt agree with the experimental data obtained by HRS measurements and further shed light on their structure-property relationship.

The elaboration of multichromophoric system which can undergo a reversible transformation over more than two different states can be easily performed by the covalent assembly of several identical switching subunits around a central node. However, the selective addressability of each of them still represents a challenging task. This study reports on the elaboration of multichromophoric systems incorporating three identical indolino-oxazolidine (BOX) moieties as multimodal addressable units. Depending of the open/closed oxazolidine ring status of each of them, these systems can be interconverted between four different states in stepwise manner by using indifferently acid addition or electrochemical stimulation. More important, we have demonstrated by using a dissymmetric triarylamine node that the classical statistical BOX opening is broken then reaching a regioselective addressability. The switching of the three identical BOX units differentiated by their π conjugated junction to the central core follows a preferential order leading to the preponderant and successive formation of only four forms over the eight theoretically and equally expected. To provide limitations and outlooks for such strategy, their switching capacities have been rationalized by DFT calculations.

The development of molecular switches such as photochromic and electrochromic systems still represents a major concern in numerous application fields. If numerous pure organic switch families have been explored so far, concerning the coordination compounds, the choice seems more limited. In this context, we are exploring the possibility to elaborate a new addressable ligand family based on benzazolo-oxazolidine (BOX) moiety, a poorly investigated switch family, known for its acido-, electro- and photochromism properties. As proof of concept, two ligands bearing a BOX moiety were prepared using a pyridine as metal binding site after what corresponding Zn(II) complexes were synthesized and characterized. The acido-, electro- and photochemical behaviors of the free ligand as well as complexes were studied. This study reveals a subtle and interesting tautomeric equilibrium between oxazolidine ring opening and pyridine protonation whatever the nature of the stimulation. More interestingly, it conducts to observe the possibility to catch and release zinc ion on demand by using two external and orthogonal stimulations.

International audience; Combining different molecular switching functions in a single molecule is a simple strategy to develop commutable molecules featuring more than two commutation states. The present study reports on two molecular systems consisting of two indolino-oxazolidine (Box) moieties connected to an aromatic bridge (phenyl or bithiophene) by ethylenic junctions. Such systems, referenced as BiBox, are expected to show up multiaddressable and multiresponsive behaviors. On one hand, the oxazolidine ring opening/closure of Box moieties can be addressed by chemical stimuli, and on the other hand, the trans-to-cis isomerization of the ethylenic junctions is induced by visible light irradiation (with a thermal back conversion). NMR and UV−visible spectroscopies allowed to characterize up to nine out of the ten theoretically expected commutation states as well as to measure the kinetics of the interconversions. Also, steady state fluorescence spectroscopy measurements highlighted the strong influence of the open/closed states of the Box moieties on their emission properties.

Over the past decade many efforts have been focused on the synthesis, modification and application of multi-responsive molecular systems. Up to now, two main strategies have been conducted to elaborate such systems: either by connecting different molecular switches through covalent links or by mixing them within supramolecular assemblies to obtain multiresponsiveness through the combination of various stimulations (i.e., photon, electron, proton, etc…). In thisthesis, we report a different approach based on the employment of identical indolinooxazolidine (BOX) unit as multi-modal switch. Indeed, the opening of the oxazolidine ring can be reversibly and selectively achieved either under UV irradiation, electrochemical stimulation or acidity changes. According to our first strategy, two BOX units were connected around a simple linear aromatic plate forms, such as bithiophene and EDOT-Thiophene-EDOT unit as spacer. Interestingly, these systems are able to commute between 3 different metastable states in a stepwise manner with all kinds of stimulations. Going further, in order to promote the metastable states, it was possible to increase the number of BOX by connecting three of them on more elaborated pi systems which are potentially able to exhibit up to four discriminate metastable states. Complementary to that, a second strategy was to synthesize various nitrogen ligands functionalized by at least one BOX unit and their coordination chemistry with zinc and ruthenium metals. The response of the ligands as well as their corresponding complexes under photo, electro and acidic stimulation were also investigated and fully characterized., Au cours des dernières décennies, de nombreux efforts se sont focalisés sur la synthèse, la modification et l’utilisation de systèmes moléculaires multi-adressables. Afin d’élaborer de tels systèmes capables de répondre à des stimulations de différentes natures (par exemple : photon, électron, proton, etc…) les deux principales stratégies consistaient à ce jour à connecter différents types d’unités stimulables soit par liaison covalente soit par dispersion au sein d’assemblages supramoléculaires. Au cours de cette thèse, nous nous sommes attachés à développer une nouvelle approche basée sur l’utilisation d’un unique switch multi-mode : les indolino-oxazolidine (BOX). En effet, cette unité est capable de commuter entre deux états métastables (ouvert et fermé) et ce de façon indifférenciée par application d’une stimulation lumineuse, électrochimique ou encore par variation du pH. En suivant une première stratégie, deux unités BOX ont été connectées via l’utilisation d’un simple système conjugué linéaire tels qu’une unité bithiophène et un enchainement EDOT-Thiophène-EDOT (ETE) comme espaceur. Nous avons démontré que ces systèmes multi-stimulables sont capables de commuter de façon pas à pas entre 3 états métastables différents et ce quel que soit la nature du stimulus. Afin de démontrer les nombreuses possibilités de cette approche et augmenter le nombre d’états métastables, 3 unités BOX ont été connectés par l’utilisation de systèmes conjugués plus élaborés permettant ainsi de conduire à des interrupteurs moléculaires capables de présenter jusqu’à 4 états différents. En complément de cette approche purement organique, une seconde stratégie a consisté à fonctionnaliser différents ligands azotés par au moins une entité BOX afin d’élaborer des systèmes plus complexes par chimie de coordination avec des ions métalliques de zinc et de ruthénium. Les ligands préparés ainsi que les complexes correspondants ont été pleinement caractérisés et leur addressabilité sous stimulation chimique, électrique et lumineuse étudiée.

The design of multistate/multifunctional molecular systems arouses a lot of interest. Such compounds are able to commutate between two metastable states by the application of an external stimulation such as light, heat, protons, or electrons. In this context, we are interested in molecular switches based on indolino-oxazolidine (BOX) which is a relatively less-known sub-class of multimodal addressable units. Their particularity consists of the possibility to induce the opening/closing of the oxazolidine ring by using indifferently light, electrochemical, or acido-basic stimulation. Up to now, most of the reported systems based on BOX have allowed to modulate a molecular property but only between two discrete levels which can only be extended by their association with other classical switchable unit such as a dithienylethene unit. For this reason, we report here our effort to enhance the number of metastable states by simply connecting two identical BOX units by a bithiophene (BT) linker. The resulting sys...

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International audience; With the view to altering the lipophilicity and electron accepting ability of the tetraphenyl-carbo-benzene scaffold, peripheral fluorination of the C18 ring through aromatic linkers was envisaged from the C18Ph6 and o-tBu2C18Ph4 references, by replacement of two Ph substituents with two p-CF3-C6H4 counterparts (FTol). The synthesis relied on a [8+10] macrocyclization involving a common bis(trifluorotolyl)-tetraynedione, followed by reductive aromatization of the resulting [6]pericyclynediols. While p-FTol2C18Ph4 proved to be hardly tractable due to an extremely low solubility, p-FTol2-o-tBu2C18Ph2 could be extensively studied by X-ray crystallography, NMR and UV/Vis spectroscopy, voltammetry, STM imaging of monolayers, and AFM imaging of binary films with P3HT or PC71BM fabricated by spin-coating for organic photovoltaic cells and J−V curve measurement thereof. The electronic and polarity properties are correlated with moderate but consistent electron-withdrawing effects of the CF3 groups, in agreement with the DFT-calculated frontier orbitals and multipole moments. The results provide guidelines for optimization of fluorinated carbo-benzene targets.

BACKGROUND Muscle transfer has been reported as a good surgical option to reconstruct the deficient rotator cuff. The purpose of this study is to report the outcome of deltoid muscle flap transfer to restore shoulder function in patients with massive irreparable rotator cuff tear. MATERIAL AND METHODS This is a retrospective descriptive case series. Included patients had a lesion of two or more tendons of the rotator cuff or lesion of one tendon of more than 5 cm in width and no lesion to the subscapularis. Evaluation was done using the Constant score, visual analog scale for satisfaction and quality of life. RESULTS Twenty patients met the inclusion criteria. Three patients were lost to follow-up. The remaining (9 males and 8 females) had a mean follow-up period of 40.5 months. The mean age at surgery was 61.3 years. Thirty-five percent of patients were involved in heavy labor while the lesions affected the dominant side in 70% of the cases. Mean preoperative Constant score was 40.8 and increased to 78.8 (p < 0.05) with a difference of +38 points on the raw Constant score and an improvement rate of 64%. The greatest improvement involved essentially pain and quality of life (improvement rate of 82%) (p < 0.05). Eighty-nine percent of patients have good and excellent self-reported results. CONCLUSION More than just a salvage procedure, deltoid muscle flap seems to be an adequate option in terms of appropriate pain relief, function recovery as well as patient satisfaction. Keywords: massive rotator cuff tears, deltoid muscle flap