Dimethylformamide dimethyl acetal reagent for in situ chiral analyses of organic molecules on Titan with the Dragonfly mass spectrometer space instrument (Dragonfly mission).

Thanks to the Cassini-Huygens space mission between 2004 and 2017, a lot was learned about Titan, the biggest satellite of Saturn, and its intriguing atmosphere, surface, and organic chemistry complexity. However, key questions about the potential for the atmosphere and surface chemistry to produce organic molecules of direct interest for prebiotic chemistry and life did not find an answer. Due to Titan potential as a habitable world, NASA selected the Dragonfly space mission to be launched in 2027 to Titan's surface and explore the Shangri-La surface region for minimum 3 years. One of the main goals of this mission will be to understand the past and actual abundant prebiotic chemistry on Titan, especially using the Dragonfly Mass Spectrometer (DraMS). Two recently used sample pre-treatments for Gas Chromatography - Mass Spectrometry (GC-MS mode of DraMS) analyses are planned prior analysis to extract refractory organic molecules of interest for prebiotic chemistry and astrobiology. The dimethylformamide dimethylacetal (DMF-DMA) derivatization reaction offers undoubtedly an opportunity to detect biosignatures by volatilizing refractory biological or prebiotic molecules and conserving the chiral carbons' conformation while an enantiomeric excess indicates a chemical feature induced primarily by life (and may be aided on the primitive systems by light polarization). The goal of this study is to investigate the ageing of DMF-DMA in DraMS (and likely MOMA) capsules prior to in situ analysis on Titan (or Mars). The main results highlighted by our work on DMF-DMA are first its satisfactory stability for space requirements through time (no significant degradation over a year of storage and less than 30 % of lost under thermal stress) to a wide range of temperature (0 °C to 250 °C), or the presence of water and oxidants during the derivatization reaction (between 0 and 10 % of DMF-DMA degradation). Moreover, this reagent derivatized very well amines and carboxylic acids in high or trace amounts (ppt to hundreds of ppm), conserving their molecular conformation during the heat at 145 °C for 3 min (0 to 4% in the enantiomeric form change).

Evaluation of the interference of Tenax®TA adsorbent with dimethylformamide dimethyl acetal reagent for gas chromatography-Dragonfly mass spectrometry and future gas chromatography-mass spectrometry in situ analysis.

Among future space missions, national aeronautics and space administration (NASA) selected two of them to analyze the diversity in organic content within Martian and Titan soil samples using a gas chromatograph - mass spectrometer (GC-MS) instrument. The Dragonfly space mission is planned to be launched in 2027 to Titan's surface and explore the Shangri-La surface region for years. One of the main goals of this mission is to understand the past and actual abundant prebiotic chemistry on Titan, which is not well characterized yet. The ExoMars space mission is planned to be launched in 2028 to Mars' surface and explore the Oxia Planum and Mawrth Vallis region for years. The main objectives focus on the exploration of the subsurface soil samples, potentially richer in organics, that might be relevant for the search of past life traces on Mars where irradiation does not impact the matrices and organics. One recently used sample pre-treatment for gas chromatography - mass spectrometry analysis is planned on both space missions to detect refractory organic molecules of interest for astrobiology. This pre-treatment is called derivatization and uses a chemical reagent - called dimethylformamide dimethyl acetal (DMF-DMA) - to sublimate organic compounds keeping them safe from thermal degradation and conserving the chirality of the molecules extracted from Titan or Mars' matrices. Indeed, the detection of building blocks of life or enantiomeric excess of some organics (e.g. amino acids) after DMF-DMA pre-treatment and GC-MS analyses would be both bioindicators. The main results highlighted by our work on DMF-DMA and Tenax®TA interaction and efficiency to detect organic compounds at ppb levels in a fast and single preparation are first that Tenax®TA did not show the onset of degradation until after 150 experiments - a 120 h at 300 °C experiment - which greatly exceeds the experimental lifetimes for the DraMS and GC-space in situ investigations. Tenax®TA polymer and DMF-DMA produce many by-products (about 70 and 46, respectively, depending on the activation temperature). Further, the interaction between the two leads to the production of 22 additional by-products from DMF-DMA degradation, but these listed by-products do not prevent the detection of trace-level organic molecules after their efficient derivatization and volatilization by DMF-DMA in the oven ahead the GC-MS trap and column.

Influence of pH and salts on DMF-DMA derivatization for future Space Applications.

For gas chromatography - mass spectrometry (GC-MS) analyses performed in situ, pH and salts (e.g., chlorides, sulfates) may enhance or inhibit the detection of targeted molecules of interest for astrobiology (e.g. amino acids, fatty acids, nucleobases). Obviously, salts influence the ionic strength of the solutions, the pH value, and the salting effect. But the presence of salts may also produce complexes or mask ions in the sample (masking effect on hydroxide ion, ammonia, etc.). For future space missions, wet chemistry will be conducted before GC-MS analyses to detect the full organic content of a sample. The defined organic targets for space GC-MS instrument requirements are generally strongly polar or refractory organic compounds, such as amino acids playing a role in the protein production and metabolism regulations for life on Earth, nucleobases essential for DNA and RNA formation and mutation, and fatty acids that composed most of the eukaryote and prokaryote membranes on Earth and resist to environmental stress long enough to still be observed on Mars or ocean worlds in geological well-preserved records. The wet-chemistry chemical treatment consists of reacting an organic reagent with the sample to extract and volatilize polar or refractory organic molecules (i.e. dimethylformamide dimethyl acetal (DMF-DMA) in this study). DMF-DMA derivatizes functional groups with labile H in organics, without modifying their chiral conformation. The influence of pH and salt concentration of extraterrestrial materials on the DMF-DMA derivatization remains understudied. In this research, we studied the influence of different salts and pHs on the derivatization of organic molecules of astrobiological interest with DMF-DMA, such as amino acids, carboxylic acids, and nucleobases. Results show that salts and pH influence the derivatization yield, and that their effect depend on the nature of the organics and the salts studied. Second, monovalent salts lead to a higher or similar organic recovery compared to divalent salts regardless of pH below 8. However, a pH above 8 inhibits the DMF-DMA derivatization influencing the carboxylic acid function to become an anionic group without labile H. Overall, considering the negative effect of the salts on the detection of organic molecules, future space missions may have to consider a desalting step prior to derivatization and GC-MS analyses.

Thermal stability of adsorbents used for gas chromatography in space exploration.

For analytical purpose, thermal desorption is now used in gas chromatographs developed to analyse the chemical composition of planetary environments. Due to technical constraints, the thermal desorption cannot be as finely controlled as in the laboratory resulting in possible thermal alteration of the adsorbents used. For these reasons, the influence of heat on physical and chemical properties of various adsorbents, either used or that could be used in gas chromatographs for space exploration, is studied. If the adsorbents made of carbon molecular sieves and graphitised carbon black that were tested show a very high thermal stability up to 800°C, the porous polymers tested are highly degraded from a minimum temperature that depends on the nature of the polymer. Poly-2,6-diphenylphenylene oxide is shown to be the more thermally robust as it is degraded at higher temperatures, confirming it is currently the best choice for analysing organic molecules with a space instrument. Finally, the products of degradation of the porous polymers tested were analysed after heating the porous polymers at 400 °C and 800 °C. They were identified and listed as potential contaminants of analyses performed with this type of adsorbent. If the exposure to the higher temperature produces numerous organic compounds, mainly aromatic ones, a few ones are also detected at the lower temperature tested, meaning they should be considered as potential contaminants. Again poly-2,6-diphenylphenylene oxide should be preferred because it releases less organic compounds, the structure of which is completely specific to the adsorbent composition.

PET/CT with 18F-Fluordesoxyglucose in patients with suspected endovascular prosthesis infection. / PET/TC con 18F-Fluordesoxiglucosa en pacientes con sospecha de infección de prótesis endovasculares.

OBJECTIVE: Infection of large vessel prostheses is a rare but critical complication. The aim of this work is to assess the impact of PET/CT with 18F-Fluordesoxyglucose (PET-FDG) on the diagnosis of infection in our environment. MATERIAL AND METHODS: Thirty-five patients (38 scans) were evaluated for suspected prosthetic infection. A qualitative analysis was performed taking into account the distribution of the radiopharmaceutical, categorizing the studies as positive or negative for infection. Those with focal or multifocal deposits along the vascular prosthesis were considered positive, and negative if a homogeneous and diffuse distribution over the whole prosthesis was observed, or a total absence of uptake. A semi-quantitative analysis was performed using SUVmax and average SUV values, and a metabolic index was calculated (SUVmax of the graft / average SUV of the normal vascular pool). RESULTS: The PET-FDG study was positive in 20 patients, with a diagnostic accuracy of 84%. The 38 PET-FDG scans performed showed positive capture patterns (focal in 6, multifocal in 15, diffuse in 4) and negative pattern in the remaining 13. The sensitivity, specificity, positive and negative predictive values obtained for the PET-FDG were 95%, 89%, 90% and 94%, and for the AngioTC study 50%, 73%, 73% and 50%, respectively. The area values under the ROC curve were as follows: for the AngioTC 0.642 (not significant), and for the SUVmax values of 0.925 (p<0.005), average SUV of 0.922 (p<0.005) and for the metabolic index of 0.917 (p<0.005). CONCLUSIONS: The PET-FDG proves to be a tool with high diagnostic accuracy in the infection of vascular prosthesis, both visual analysis according to patterns and semi-quantitative.

Application of TMAH thermochemolysis to the detection of nucleobases: Application to the MOMA and SAM space experiment.

Thermochemolysis of seven nucleobases-adenine, thymine, uracil, cytosine, guanine, xanthine, and hypoxanthine-in tetramethylammonium hydroxide (TMAH) was studied individually by pyrolysis gas chromatography mass spectrometry in the frame of the Mars surface exploration. The analyses were performed under conditions relevant to the Sample Analysis at Mars (SAM) instrument of the Mars Curiosity Rover and the Mars Organic Molecule Analyzer (MOMA) instrument of the ExoMars Rover. The thermochemolysis products of each nucleobase were identified and the reaction mechanisms studied. The thermochemolysis temperature was optimized and the limit of detection and quantification of each nucleobase were also investigated. Results indicate that 600°C is the optimal thermochemolysis temperature for all seven nucleobases. The methylated products trimethyl-adenine, 1, 3-dimethyl-thymine, 1, 3-dimethyl-uracil, trimethyl-cytosine, 1, 3, 7-trimethyl-xanthine (caffeine), and dimethyl-hypoxanthine, respectively, are the most stable forms of adenine, thymine, uracil, cytosine, guanine, and xanthine, and hypoxanthine in TMAH solutions. The limits of detection for adenine, thymine, and uracil were 0.075 nmol; the limits of detection for guanine, cytosine, and hypoxanthine were higher, at 0.40, 0.55, and 0.75 nmol, respectively. These experiments allowed to well constrain the analytical capabilities of the thermochemolysis experiments that will be performed on Mars to detect nucleobases.

In-continuity neuroma of the median nerve after surgical release for carpal tunnel syndrome: case report.

Iatrogenic injuries of the median nerve after surgical release for carpal tunnel syndrome resulting in the formation of a neuroma are rare. We present here the case of two patients, one with a bifid median nerve, showing in-continuity neuroma after surgical release for carpal tunnel syndrome. The patients reported persistent post-operative pain and showing symptoms. In both cases, ultrasound showed an in-continuity neuroma with a hypoechoic and enlarged median nerve at the carpal tunnel. The case report shows that ultrasound may be helpful in confirming the clinical diagnosis of neuroma and it is useful for evaluation of the percentage of the area affected by the tear.

Gas chromatography for in situ analysis of a cometary nucleus V. Study of capillary columns' robustness submitted to long-term reduced environmental pressure conditions.

With the European Space Agency's Rosetta space mission to comet 67P/Churyumov-Gerasimenko, a gas chromatograph, part of the COmetary Sampling And Composition (COSAC) experiment, travelled for about 10 years in the interplanetary medium before operating at the surface of the cometary nucleus in November 2014. During its journey in space, the instrument was exposed to the constraining conditions of the interplanetary medium, including reduced environmental pressures. In order to estimate the potential influence of this severe condition on the chromatographic capillary columns, their stationary phase and the subsequent separation capability, a set of flight spare columns were kept under reduced environmental pressure in the laboratory for the same duration as the probe sent to the comet. The columns' analytical performances were evaluated recently and compared to the original ones obtained just before the launch of the Rosetta probe. The results presented here show that the chromatographic performances of the spare chromatographic columns were not altered in time. From this result, it can be expected that the flight instrument will perform nominally for the analysis of the first cometary nucleus sample to be collected ever, and that the preparation of the interpretation of the data to be taken at the cometary surface nucleus can be done through calibration of these spare columns, and other spare components of the instrument.

Septic complications involving hand and wrist in patients with pre-existing rheumatoid arthritis: The role of magnetic resonance imaging and sonography.

PURPOSE: Septic arthritis (SA), frequently involving hand and wrist, is common in rheumatoid arthritis (RA) patients due to immunomediated etiology of RA and immunosuppressive drug use. Clinical and laboratory features might not be useful to differentiate between RA relapse and superimposed SA. The role of magnetic resonance imaging (MRI) has been described in several studies. Our aim is to evaluate the role of ultrasonography (US). MATERIAL AND METHODS: In the last 4 years 31 MRI of hand and wrist has been performed in the suspect of SA complicating RA. A 1.5 T unit (Siemens Symphony, Erlangen, Germany) with standardized protocol, involving the administration of contrast medium, was used. Also US with power Doppler evaluation was performed. A Philips IU22 US scanner was used. RESULTS: Eleven points (according to Graif's study) were analyzed for every MRI and US. At MRI joint effusion (37.5% of RA relapse vs 100% superimposed SA) and soft tissue edema (25% vs 100%) were indicative of SA. At US joint effusion (31.3% of RA relapse vs 73.3% superimposed SA) and soft tissue edema (12.5% vs 60%) were indicative of SA. CONCLUSION: Our results suggest that joint effusion and soft tissue edema are markers suggestive for superimposed SA and that MRI is more sensitive in their evaluation. Although US is less sensitive than MRI, the former is important in guiding invasive procedure and evaluating patients that cannot undergo MRI.

Enthesitis of the direct tendon of the rectus femoris muscle in a professional volleyball player: A case report.

Enthesitis of the direct tendon of the rectus femoris muscle is a rare pathology which mainly affects professional athletes, and it is caused by overuse and repetitive microtrauma. Athletic jumping and kicking exert a great stress on the direct tendon of the rectus femoris muscle, and volleyball and football players are therefore most frequently affected. Enthesitis may occur suddenly causing pain and functional impairment possibly associated with partial or complete tendon injuries, or it may be a chronic condition causing non-specific clinical symptoms.We present the case of a professional volleyball player who felt a sudden pain in the left side of the groin area during a training session although she had suffered no accidental injury. The pain was associated with impaired ipsilateral limb function. Tendon rupture was suspected, and magnetic resonance imaging (MRI) was performed. MRI showed a lesion at the myotendinous junction associated with marked inhomogeneity of the direct tendon. Ultrasound (US) examination confirmed the presence of both lesions and allowed a more detailed study of the pathology.This is a typical case of enthesitis which confirms that MRI should be considered the examination of choice in hip pain, particularly when the patient is a professional athlete, thanks to its panoramic visualization. However, also US is an ideal imaging technique for evaluating tendon injuries thanks to its high spatial resolution, and it can therefore be used effectively as a second line of investigation.

Ultrasound guided fine-needle aspiration cytology of breast lesions.

Breast biopsy consists in the collection of cells or tissue fragments from a breast lesion and their analysis by a pathologist. There are several types of breast biopsy defined on the basis of the type of needle used: fine-needle aspiration and biopsy performed with a spring-based needle. This article focuses on fine-needle aspiration performed under sonographic guidance.It is used mainly to assess cysts that appear to contain vegetations or blood or that are associated with symptoms; lesions and solid nodules that are not unequivocally benign; and axillary lymph nodes that appear suspicious on physical examination and/or sonography.In addition to distinguishing between benign and malignant lesions, ultrasound guided fine-needle aspiration also plays an important role in tumor grading and in immunocytochemical identifying specific tumor markers. This article describes the technique used and the possible causes of false negative and false positive findings. Despite its limitations, fine-needle aspiration has become a fundamental tool for the identification and preoperative management of malignant breast lesions.

Recurrence of giant juvenile breast fibroadenoma in a girl with Turner's syndrome.

Pathological breast conditions are rare in childhood and adolescence. The spectrum of breast disease in pediatric patients is different from that in adults and most lesions are benign. Fibroadenomas are the most common type of breast tumor in adolescent girls and young women. These lesions occasionally develop into very large masses, particularly in adolescent girls. Such masses are called solitary giant juvenile fibroadenomas, and local recurrence is unusual. We report here a case of recurrent juvenile giant breast fibroadenoma in a girl with Turner's syndrome.

Overload syndromes of the knee in adolescents: Sonographic findings.

Overload syndromes are caused by repetitive microtrauma, and the knee joint is most frequently affected in adolescents. The reason for this is that the knee joint is engaged in almost all sports activities. Pathologies related to the anterior aspect of the knee are: femoropatellar pain, jumper's knee syndromes, Osgood-Schlatter disease, Sinding-Larsen-Johansson syndrome and patellar stress fractures; to the medial aspect: semimembranous tendon enthesopathy and pes anserinus bursitis; to the lateral aspect: iliotibial band syndrome (runner's knee), popliteus and femoral biceps tendon enthesopathy; to the posterior aspect: fabella syndrome and medial gastrocnemius muscle tendon enthesopathy. Sonography plays a central role in the diagnosis and can also evaluate the evolution of diseases. This method is well accepted by the patients and by their parents, it does not involve exposure to X-rays and it is inexpensive. US imaging should, therefore, be considered a first-line imaging diagnostic technique in functional overuse syndromes of the knee.

Complex organic matter in Titan's atmospheric aerosols from in situ pyrolysis and analysis.

Aerosols in Titan's atmosphere play an important role in determining its thermal structure. They also serve as sinks for organic vapours and can act as condensation nuclei for the formation of clouds, where the condensation efficiency will depend on the chemical composition of the aerosols. So far, however, no direct information has been available on the chemical composition of these particles. Here we report an in situ chemical analysis of Titan's aerosols by pyrolysis at 600 degrees C. Ammonia (NH3) and hydrogen cyanide (HCN) have been identified as the main pyrolysis products. This clearly shows that the aerosol particles include a solid organic refractory core. NH3 and HCN are gaseous chemical fingerprints of the complex organics that constitute this core, and their presence demonstrates that carbon and nitrogen are in the aerosols.

Gas chromatography for in situ analysis of a cometary nucleus. IV. Study of capillary column robustness for space application.

As part of the development of the European Space Agency Rosetta space mission to investigate a cometary nucleus, the selection of columns dedicated to the gas chromatographic subsystem of the Cometary Sampling and Composition (COSAC) experiment was achieved. Once the space probe launched, these columns will be exposed to the harsh environmental constraints of space missions: vibrations, radiation (by photons or energetic particles), space vacuum, and large temperature range. In order to test the resistance of the flight columns and their stationary phases, the columns were exposed to these rough conditions reproduced in the laboratory. The comparison of the analytical performances of the columns, evaluated prior and after the environmental tests, demonstrated that all the columns withstand space constraints, and that their analytical properties were preserved. Therefore, all the selected capillary columns, even having porous layer or chiral stationary phases, were qualified for space exploration.

Gas chromatography for in situ analysis of a cometary nucleus III. Multi-capillary column system for the cometary sampling and composition experiment of the Rosetta lander probe.

The cometary sampling and composition (COSAC) experiment is one of the principal experiments of the surface lander probe of the European Space Agency Rosetta mission to be launched in January 2003. The instrument is designed for the in situ chemical analysis of a cometary nucleus as the details of the nucleus composition are of primary importance for understanding both the formation of the solar system, and the origin of life on Earth. The COSAC experiment consists of an evaporation/pyrolysis device and two analytical systems: a multi-column gas chromatograph and a high-resolution time-of-flight mass spectrometer which may either be operated alone or in a coupled mode. The gas chromatograph includes five general purpose chromatographic columns and three chiral ones, all mounted in parallel. Taking into account the chemical species potentially present in the cometary nucleus as well as the space constraints, a set of five complementary columns was selected to perform the separation and identification of the compounds present in the cometary nucleus. This set of columns includes a carbon molecular sieve porous-layer open tubular (PLOT) column used for the separation of both the noble and other permanent gases, and the C1-C2 hydrocarbons. A second PLOT column uses a divinylbenzene-ethylene glycol-dimethylacrylate porous polymer as stationary phase for the analysis of a wide range of C1-C2 organic molecules, Two complementary wall-coated open tubular (WCOT) columns with polydimethylsiloxane (PDMS) liquid stationary phases, one containing cyanopropyl-phenylsiloxane and the other diphenylsiloxane groups, are designed to target the same range of organic compounds (C3-C7) which could be representative of the widest range of cometary compounds. A third WCOT column with an apolar stationary phase made of non-substituted PDMS is used for the separation and identification of higher-molecular-mass compounds (up to C10) and aromatic species (monoaromatic and polyaromatic). This paper describes these five general-purpose capillary PLOT and WCOT columns, selected to be used in the COSAC GC system. The analytical capabilities are examined with a special emphasis on the exobiological and planetological implications.