Phthalocyanine-based field-effect transistors as gas sensors

International audienceIn this review, a description of molecular field-effect transistors is given, in comparison with gate-modified inorganic counterparts. The different processes involved in gas sensing are summarized. The advantages of transistors on resistors are demonstrated. Sensitivity of molecular field-effect transistors to strong oxidizing species like ozone is detailed and compared to their sensitivity to humidity and volatile organic compounds. Application to ozone monitoring in urban atmosphere is also presented

Développement d'un capteur de gaz à transduction microonde

Ce mémoire présente les recherches effectuées sur une nouvelle méthode de transduction, exploitant la propagation des ondes àhaute fréquence, pour la détection de polluants atmosphériques. Dans un premier temps, les principaux modes de transduction exploités dans les capteurs existants sont présentés. Ils fonctionnent dans des gammes de fréquences différentes des microondes, afin de comprendre ce que peut apporter cette nouvelle transduction. La permittivité diélectrique est le principal paramètre physique responsable de la détection microonde. Cependant, la variation de la conductivité du matériau sensible modifie également la transmission de l'onde à travers le dispositif microonde. Les propriétés de propagation d'une onde sont formulées afin de comprendre comment l'onde est influencée par la propagation dans le matériau sensible et comment sa mesure est effectuée. Le traitement des données joue un rôle important dans la détermination de la réponse des capteurs. Les matériaux inorganiques (oxydes d'étain et de titane) ont permis de valider les modes de transduction. Différentes géométries de capteurs ont été modélisées et utilisées avec des poudres compressées et des films minces, en particulier avec un matériau moléculaire (phtalocyanine de cobalt). Ces études nous ont permis d'améliorer la transduction, grâce à l'évolution du format de la structure microonde. Cette évolution a permis d'obtenir une discrimination meilleure que 100 ppm pour l'ammoniac dans l'argon ou dans l'air, et ce à température ambiante.In this work, we have developed a new gas-sensing transduction based on the propagation of microwave inside a sensitive material to detect atmospheric pollutants at room temperature. First, we present a short overview of the main gas-sensing transduction in the litterature. These techniques operate in frequency ranges different from microwaves. The dielectric permittivity is the main physical parameter in the microwave transduction. The principle is based on the excitation of a sensitive material by a microwave electromagnetic field in a propagative structure. The reflected wave is specific to the excitation's frequency. It depends on the interaction between the sensitive material and the pollutant gas and also on the geometry of the sensor. However, the variation of the conductivity of the sensitive material also changes the transmission of the wave through the microwave device. Inorganic materials (tin and titanium oxides) are used to validate the methods of transduction. Different geometries of sensor are studied with electromagnetic modeling and experimental testing. The sensitive material is used in compressed powders and thin films, in particular with a molecular material (cobalt phthalocyanine). This work improves the microwave transduction knowledge by the sensor geometries. The experimental tests in argon flux conduct to obtain a resolution better than 100 ppm. Few results are presented in air flux.DIJON-BU Doc.électronique (212319901) / SudocSudocFranceF

Improvement in real time detection and selectivity of phthalocyanine gas sensors dedicated to oxidizing pollutants evaluation

International audienceA sensor microsystem prototype, using copper phthalocyanine thin film as sensitive layer, and dedicated to ozone evaluation, was developed. The methodology implemented is based on cyclic sensor recalibrations by thermal cleaning of the sensitive membrane, and on pollutant concentration quantification according to the kinetics of sensor response. Results of laboratory experiments for various NO2 and O3 concentrations, in the range of 10–200 ppb, illustrate the selectivity of CuPc sensors towards ozone, obtained by our methodology. We have shown that ozone selectivity is especially improved for short time of exposure (few minutes) and for phthalocyanine layer maintained at low temperature (80 °C). For optimal conditions, our microsystem exhibits a threshold lower than 10 ppb, a resolution lower than 10 ppb, and good reproducibility of measurements. Performances obtained in real urban atmosphere are satisfying to ensure real time evaluation of ozone during several days. Long-term stability and the detection of NO2 by associating chemical filters to our microsystem will be also discussed

Druggable Nucleolin Identifies Breast Tumours Associated with Poor Prognosis That Exhibit Different Biological Processes

Background: Nucleolin (NCL) is a multifunctional protein with oncogenic properties. Anti-NCL drugs show strong cytotoxic effects, including in triple-negative breast cancer (TNBC) models, and are currently being evaluated in phase II clinical trials. However, few studies have investigated the clinical value of NCL and whether NCL stratified cancer patients. Here, we have investigated for the first time the association of NCL with clinical characteristics in breast cancers independently of the different subtypes. Methods: Using two independent series (n = 216; n = 661), we evaluated the prognostic value of NCL in non-metastatic breast cancers using univariate and/or multivariate Cox-regression analyses. Results: We reported that NCL mRNA expression levels are markers of poor survivals independently of tumour size and lymph node invasion status (n = 216). In addition, an association of NCL expression levels with poor survival was observed in TNBC (n = 40, overall survival (OS) p = 0.0287, disease-free survival (DFS) p = 0.0194). Transcriptomic analyses issued from The Cancer Genome Atlas (TCGA) database (n = 661) revealed that breast tumours expressing either low or high NCL mRNA expression levels exhibit different gene expression profiles. These data suggest that tumours expressing high NCL mRNA levels are different from those expressing low NCL mRNA levels. Conclusions: NCL is an independent marker of prognosis in breast cancers. We anticipated that anti-NCL is a promising therapeutic strategy that could rapidly be evaluated in high NCL-expressing tumours to improve breast cancer management

Alteration of ribosome function upon 5-fluorouracil treatment favors cancer cell drug-tolerance.

Mechanisms of drug-tolerance remain poorly understood and have been linked to genomic but also to non-genomic processes. 5-fluorouracil (5-FU), the most widely used chemotherapy in oncology is associated with resistance. While prescribed as an inhibitor of DNA replication, 5-FU alters all RNA pathways. Here, we show that 5-FU treatment leads to the production of fluorinated ribosomes exhibiting altered translational activities. 5-FU is incorporated into ribosomal RNAs of mature ribosomes in cancer cell lines, colorectal xenografts, and human tumors. Fluorinated ribosomes appear to be functional, yet, they display a selective translational activity towards mRNAs depending on the nature of their 5'-untranslated region. As a result, we find that sustained translation of IGF-1R mRNA, which encodes one of the most potent cell survival effectors, promotes the survival of 5-FU-treated colorectal cancer cells. Altogether, our results demonstrate that "man-made" fluorinated ribosomes favor the drug-tolerant cellular phenotype by promoting translation of survival genes

Hybrid and 2D nanomaterials

International audienceIn order to still improve the performances of chemical sensors, numerous hybrid materials were synthesized that combined at least two types of materials reported in the three previous chapters. We will distinguish materials combining macrocyclic molecules with polymers, those in which these molecules are associated to carbonaceous materials, mainly carbon nanotubes (CNTs) and graphene, and organic-inorganic hybrid materials. In this chapter, we will also include 2D materials introduced recently as sensing materials after the huge development of graphene and graphene oxide-based materials

Effet de l'humidité sur la réponse à l'ammoniac de capteurs conductimétriques à base de matériaux moléculaires

De nombreux capteurs d'ammoniac existent, mais la prise en compte de l'effet de l'humidité sur la mesure capteur est rarement assurée, y compris chez les fabricants. L'objectif de cette thèse est de proposer un transducteur conductimétrique capable de mesurer le taux d'ammoniac de façon sélective, avec une précision suffisante, pour une application au contrôle de la qualité de l'air dans un environnement à taux d'humidité variable. Le moyen employé pour atteindre cet objectif est l'utilisation de résistors à base de phtalocyanines de cobalt, sous forme de films minces, comme matériaux semi-conducteurs. L'étude porte sur la mise en forme de ces films minces réalisés par évaporation sous vide, évaporation de solvant et électrodéposition. Des bancs de mesures automatisés ont été mis en place pour effectuer les mesures électriques sous argon et pour étudierles réponses à l'ammoniac sec ou humide en appliquant des cycles exposition / repos. A partir de ces cycles de 1 min et 4 min, des réponses relatives sont calculées pour obtenir des valeurs proportionnelles aux concentrations d'ammoniac. Les effets de l'humidité seule et de l'ozone ont également été étudiés. Des tests sur la sensibilité croisée ammoniac / humidité ont été réalisés sur quatre résistors différents, dans des gammes de concentration allant de 25 à 90 ppm et dans des gammes d'humidité allant de 0 à 80% d'HR, à température ambiante. Deux d'entre eux, un résistor de phtalocyanine de cobalt (PcCo) et un résistor hybride de phtalocyanine de cobalt sulfonée /polypyrrole (s-PcCo/PPy), ont donné des résultats particulièrement intéressants.PcCo permet de discriminer des concentrations de 25, 45 et 90 ppm d'ammoniac dans une gammede 20 à 60% d'HR, avec une réponse relative de 40% à 45 ppm. De plus, mêmes si les RRs à 80%d'HR divergent légèrement, la discrimination est toujours possible entre les différentesconcentrations de NH3.s-PcCo / PPy est moins sensible à l'ammoniac, mais son étude a permis de démontrer que l'ajout dephtalocyanine dans une matrice polypyrrole augmente la sensibilité de ce matériau. Il donne uneréponse relative de 3,3% à 45 ppm. Cependant, la gamme d'humidité couverte est plus large, allant de 20 à 80% d'HR.Cette étude a donc permis de comparer des matériaux et d'estimer leur potentiel pour des applications au contrôle de la qualité de l'air avec différents taux d'humiditéMany ammonia sensors are available but the consideration of the humidity effect is scarcely insured even by manufacturers. The aim of this thesis is to propose a conductimetric transducer capable tomeasure ammonia selectively, with enough accuracy for air quality control, in a variable humidity environment. To reach this goal, we used thin film resistors made of cobalt phthalocyanines as semiconductor. This study deals with thin films processing made by vacuum evaporation, solventcast and electrodeposition. Automated workbenches were developed to perform electrical measurements under argon and to study the response of sensors to dry or humid ammonia by meansof 1 min / 4 min-long exposure / recovery cycles. From those cycles, relative responses are calculated to obtain values proportional to ammonia concentrations. The humidity and ozone effects are also studied independently as well. Ammonia / humidity cross sensitivity tests are made with four different resistors exposed to ammonia concentration in a 25-90 ppm range and in a 0-80%relative humidity range, under ambient temperature. Two of them, a cobalt phthalocyanine (CoPc)resistor and a hybrid resistor made of sulfonated cobalt phthalocyanine / polypyrrole (s-CoPc/PPy)gave interesting results.CoPc allows to discriminate 25, 45 and 90 ppm ammonia concentrations under 20-60% RH range,with a relative response of 40% at 45 ppm. Moreover, even if the RRs at 80% RH shift slightly, it isstill possible to discriminate the different concentrations.s-CoPc / PPy is less sensitive to ammonia but its study allowed to show that adding phthalocyaninein a PPy matrix enhances the sensitivity of this material and gives a RR of 3.3% at 45 ppm.However, the covered humidity range is larger, from 20 to 80% RH. Thus, this study allows to compare molecular materials and estimate their potential for air quality control applications with different humidity levelsDIJON-BU Doc.électronique (212319901) / SudocSudocFranceF