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Methods for reduction of volatile organic compounds (VOCs) content in air depend on the application considered. For low concentration and low flux, nonthermal plasma methods are often considered as efficient. However, the complex chemistry involved is still not well understood because there is a lack of data sets of byproducts formation. To overcome this issue, rapid analytical methods are needed. We present the coupling of a rapid chemical ionization mass spectrometer (CIMS) for the real-time analysis of the VOCs formed during a degradation experiment. The high-resolution instrument used allows for chemical ionization and direct quantification of nontargeted compounds. This method is successfully applied to degradation experiments of acetone in a phototriggered nitrogen plasma discharge. Two regimes were highlighted: efficient conversion at low concentrations (100 ppm) and moderate efficiency conversion at higher concentrations (100 ppm). Those two regimes were clearly delimited as the sum of two exponential curves occurring at respectively low and high concentrations. Many byproducts were detected; in particular, HCN presented a significantly high yield. Nitrile compounds (acetonitrile, propionitrile, ...) are formed as well. To a lower extent, ketene, acetaldehyde, and formaldehyde are observed. The association of the high-resolution mass spectrometer to the plasma reactor will allow further insights into the plasma chemistry and comparison to modelization.

International audience; We compare the predictions of our recently developed statistical molecular fragmentation (SMF) model with experimental results from plasma induced hydrocarbon decay. The SMF model is an exactly solvable statistical model, capable to calculate the probabilities for all possible fragmentation channels as a function of the deposited excitation energy. The weights of the channels are calculated from the corresponding volume of the accessible phase space of the system, taking into account all relevant degeneracies, symmetries and density functions. An experiment designed to study the abatement of propene in N 2 using a photo-triggered discharge producing a homogeneous plasma at sub-atmospheric pressure was also performed. Using a 0D model that simulates the complex chemical kinetics in the plasma, it was possible to assess the percentages of the original parent hydrocarbon's fragmentation channels based on the detected species. These results were compared to those obtained from the SMF model. Previous plasma induced hydrocarbon fragmentation experiments for ethene, ethane and propane, where also compared to the predictions of the SMF model. For energies below that of metastable dinitrogen (i.e. below 6.17 eV and 8.4 eV), the SMF model and the experimental fragmentation channels coincide. This study allows one to draw conclusions both on the range of excitation energies transferred to the parent hydrocarbon molecules during plasma discharge and on the probability of the dynamical coupling of two H atoms from neighbouring carbon atoms to form H 2 molecules.

The DHAP regimen (high-dose cytarabine in combination with dexamethasone and cisplatin) with or without rituximab (DHAP+/−R) is one of the most common regimens in daily practice. It is considered the standard treatment for relapse or refractory Hodgkin’s and non-Hodgkin’s lymphoma (NHL). Cisplatin nephrotoxicity is a major concern, and other platinum compounds are being tried. We performed a monocentric retrospective analysis to evaluate the use of carboplatin, so-called DHAC+/−R regimen. The purpose was to assess the toxicity of the DHAC+/−R regimen in real-life. The Dexamethasone, Cytarabine, Carboplatin (DHAC) regimen consisted of carboplatin AUC = 5 mg/ml/min (targeted area under the curve with Calvert’s formula) on day 1, cytarabine 2 g/m2 twice a day on day 2 and IV dexamethasone 40 mg from days 1 to 4. Rituximab was administrated at 375 mg/m2 on day 1 for CD20+ NHL. The interval between courses was 21 days. During the period considered, 199 patients received DHAC+/−R. For the entire cohort, median follow-up is 24 months (range, 2–82), median OS is not reached (NR), estimated 2-year OS is 75% (95% CI, 69–83) and median progression-free survival (PFS) is 46 months (95% CI, 22-NA). Of 144 patients scheduled for autologous stem cell transplantation (ASCT), 102 (71%, NA = 2) were in response after DHAC+/−R and all except 4 underwent ASCT. Grade ≥ 3 haematological toxicities were mainly thrombocytopenia (n = 101) and anaemia (n = 95). Grade ≥ 3 neutropenia occurred in 10 patients. No grade ≥ 3 renal and one grade 3 neurological toxicity were reported. DHAC+/−R is feasible in daily practice, provides good response rates and jeopardises neither stem cell collection nor ASCT.

Resume Deux cas de syndrome de Cockayne (CS) sont decrits dans une fratrie : ce diagnostic a ete suggere par des signes de neuropathie demyelinisante a l’electromyogramme dans un contexte clinique compatible. Le CS est une maladie genetique rare de pronostic severe dont la variabilite phenotypique explique la difficulte du diagnostic precoce. A propos de ces deux cas et a la lumiere de la litterature, les criteres diagnostiques definis jusqu’a present sont revus. Ceux-ci ne paraissent ni specifiques ni precoces ; l’atteinte multi-systemique et sensorielle peut faire errer la recherche diagnostique. Certaines anomalies neuroradiologiques sont evocatrices mais peuvent etre retardees. D’autres criteres diagnostiques, notamment une neuropathie peripherique demyelinisante, pourraient orienter le diagnostic. Leur importance reste a preciser par des etudes tenant compte de la cinetique d’apparition des symptomes, non seulement pour permettre un conseil prenatal, mais aussi pour evaluer l’efficacite d’eventuelles therapeutiques.

Gaseous naphthalene has been removed by air plasma generated by pulsed corona discharges at 100 °C (LSPM) and dielectric barrier discharges (DBD) up to 250 °C (LPGP) in different reactors geometries. Naphthalene has been chosen as one of unburned hydrocarbon present in exhaust gas engine during the cold start of vehicles. The comparison between the different discharge geometries has been possible using the specific input energy (SIE) as relevant parameter for pollutant removal process control considering the differences in the electrical characteristics and the differences of gas flow. The best naphthalene degradation is obtained in the wire-to cylinder (WTC) corona discharge and the stem-to-cylinder DBD with an energy cost β respectively of 10 and 20 J L−1. The main by-products issues of the naphthalene oxidation are CO2 and CO reaching 45% in Multi-Pin-to-Plan corona discharge. We detected polyaromatic hydrocarbons in the gas phase (few ppm) and in the solid phase deposited in the reactors. The introduction of water in the discharges promotes the naphthalene degradation by OH-atom, which has better oxidising power than O-atom in dry air.

We have compiled, collected, and analyzed 31 temperature–depth profiles from boreholes in the Atacama Desert in central and northern Chile. After screening these profiles, we found that only nine profiles at four different sites were suitable to invert for ground temperature history. For all the sites, no surface temperature variations could be resolved for the period 1500–1800. In the northern coastal region of Chile, there is no perceptible temperature variation at all from 1500 to present. In the northern central Chile region, between 26 and 28∘ S, the data suggest a cooling from ≈ 1850 to ≈ 1980 followed by a 1.9 K warming starting ≈ 20–40 years BP. This result is consistent with the ground surface temperature histories for Peru and the semiarid regions of South America. The duration of the cooling trend is poorly resolved and it may coincide with a marked short cooling interval in the 1960s that is found in meteorological records. The total warming is greater than that inferred from proxy climate reconstructions for central Chile and southern South America, and by the PMIP3-CMIP5 surface temperature simulations for the north-central Chile grid points. The differences among different climate reconstructions, meteorological records, and models are likely due to differences in spatial and temporal resolution among the various data sets and the models.

Background Subcutaneous (s.c.) administration of bortezomib is the most widely used route of administration for the treatment of patients with multiple myeloma. No study has as yet prospectively evaluated home versus hospital administration of s.c. bortezomib with respect to patient preference and cost. Patients and methods In this prospective trial, myeloma patients received the first administration of s.c. bortezomib of each cycle in the outpatient unit of the Department of Hematology. When possible, all subsequent doses of bortezomib within each cycle were provided at home. A cost analysis was carried out to compare the average cost of an injection of bortezomib in the outpatient unit and at home. In order to compare hospital and home administration of bortezomib for preference and satisfaction, patients had to complete 2 simple questionnaires analyzing 16 criteria, such as quality of life, well-being, social life, satisfaction, safety, quality of care, the reduction in personal transportation time, and personal anxiety. Each item was analyzed using a Likert scale. Results Fifty patients were studied. Overall, a total of 1043 s.c. injections of bortezomib were carried out, 655 (62.8%) at home, and 388 (35.2%) in the outpatient unit. The cost analysis showed that the total cost of one s.c. injection of bortezomib in the outpatient unit was e1510.09 versus e1224.57 for the home administration, which represents a reduction of e285.52, i.e. 20% of the cost of the hospital administration. The evaluation of patient preference and satisfaction showed that home administration improved the quality of life in 84% of the patients, increased well-being in 78%, and improved the activities of daily living in 72% of the cases. Overall, 98% of the patients noted their preference for home administration over the hospital administration of bortezomib. Conclusion Home administration of s.c. bortezomib is cost-effective and is preferred by myeloma patients compared with hospital administration.

The proton transfer reaction mass spectrometry (PTR-MS) is used to follow the toluene concentration at the exit of a dielectric barrier discharge, for an inlet gas mixture of dry air with organic molecules at a concentration in the range 10–100 ppm, at atmospheric pressure and room temperature. The precursor ion is H3O+, and toluene is detected at mass 93 u, corresponding to the (C6H5CH3)–H+ ion. The PTR-MS is used together with optical absorption spectroscopies to follow ozone and carbon dioxide molecules. Two different discharge regimes are studied: without or with significant self-warming effects. The PTR-MS diagnostic appears as a very useful tool for precise monitoring of the concentration of this organic molecule, and to get real-time information about the energy efficiency for the removal of the pollutant during the discharge operation, as function of the discharge regime.

Improving oil recovery in mature carbonate reservoirs is challenging due to inherent harsh conditions, i.e. high temperature, salinity and divalent ion concentration. This paper reports the development of a surfactant formulation that injected in sea water resulted in an incremental oil recovery higher than 20% at 120°C in carbonate field rocks. A systematic study comprising blend and salinity scans of a lineal alkyl benzene sulfonate (ABS) and a co-surfactant was done in order to select a suitable formulation optimized to be injected in sea water. The formulation performance was evaluated by measuring the solubility, interfacial tension (IFT) and phase behavior. The robustness of the formulation was assessed by changing the surfactant concentration and the brine salinity. Sandpack experiments with the addition of tracers were performed to determine the dynamic adsorption and coreflood experiments in low permeability reservoir cores were conducted to determine the injectivity, incremental oil recovery and surfactant adsorption/retention. The formulation was designed by blending at different ratios lipophilic surfactants that reduce the oil/water IFT with more hydrophilic co-surfactants that improve the solubility. The obtained formulation, comprising an ABS and a co-surfactant, was stable at ambient temperature and 120°C. It was optimized to be injected at sea water salinity providing ultra-low IFT ( In order to reduce surfactant losses, an optimization step consisting on the addition of a mineral oil and/or a low MW polymer was faced. A substantial reduction on adsorption/retention, maintaining incremental oil recovery values, was achieved by adding a specific amount of a specific mineral oil and/or a low MW polymer. The results presented show a robust formulation able to produce high incremental oil recovery under harsh carbonate reservoir conditions.

International audience; The present work is devoted to the precise spatiotemporal mapping of the absolute density of Ar(1s(5)) in a ns-pulsed argon plasma jet. The plasma impinges on glass and alumina targets at floating potential placed 5mm away from the reactor's nozzle. Under these conditions, diffuse discharges are established in the small gas gap. As so, the line-of-sight absolute density of Ar(1s(5)) is effectively evaluated via laser absorption spectroscopy. The application of the Abel-inversion is also demonstrated for different operating conditions leading to the precise radial mapping of the Ar(1s(5)) absolute density. The influence of each target is studied for two gas flow rates, 0.3 and 0.4lmin(-1). The temporal density profiles over a voltage pulse period reveal two maxima related with the Ar(1s(5)) production in the streamer head and in the residual diffuse plasma channel. Furthermore, the maximum Ar(1s(5)) axial/radial density (approximate to 10(13)-3.5x10(14)cm(-3)) depends on the target material and gas flow rate. Finally, the plasma is proved to be very effective for the fast desorption of organic molecules (bibenzyl) deposited on both targets. The results obtained suggest that the desorption of bibenzyl is due to the production of high Ar(1s(5)) densities at the close vicinity of the targets. [GRAPHICS] .

International audience; Allogeneic stem cell transplantation (allo-SCT) has become an essential component of the treatment for a variety of diseases in pediatric patients. During the past decades, advances in the transplant technology, availability of hematopoietic stem cells and supportive care not only have resulted in improved outcomes, but also have expanded the transplant options. However, these features have been studied mainly in adult populations. This investigation analyzed changes in patient profile, transplantation, graft characteristics and outcome among 250 children and adolescent patients who received allo-SCT in a single center between 1983 and 2010. In the 2000–2010, compared with the 1983–1999 period, a significantly higher 5-year overall survival (64% versus 52%, P=0.03) was observed together with a significant decrease of non-relapse mortality (27% versus 9%, P=0.0002). The progression-free survival was comparable between the two periods (49% versus 57%; P=0.17). The 5-year cumulative incidence of relapse was 24% between 1983 and 1999, and 34% between 2000 and 2010 (P=0.08). Major advances in supportive care practice have been made over the past decade, resulting in a significant survival benefit for the pediatric population undergoing allo-SCT. However, post-transplant relapse remains the leading cause of failure of this therapeutic approach, and preventing relapse represents a major challenge today

This paper deals with the ethanol (EtOH) removal in both dry and humid air fed dielectric barrier discharges. The experimental results were compared to the predictions of a zero dimension kinetic model to elucidate the main chemical routes occurring in the plasma phase. This comparison shows that both the dissociative quenching of the nitrogen metastables and the oxidation reactions by the oxygen atom or the hydroxyl radical should be taken into account to explain the EtOH abatement in these kinds of discharges. The CH3CHOH radical seems to be the main product of the nitrogen dissociative collisions, whereas radicals issued from the α- and β-H atom cleavage are the dominant ethanol oxidation by-products. These radicals account for the production of acetaldehyde, the main by-product of the ethanol/air fed discharges investigated here. Apart the complete oxidation products, i.e. carbon oxides and water, aldehydes containing up to six carbon atoms, ketones, carboxylic acids, ozone, nitrogen oxides, nitric acid and organic nitrates were found in the exhaust gas. A kinetic pathway is proposed to explain the formation of the detected by-products. Water vapour addition to the feeding gas slightly improves the EtOH removal and promotes further oxidation of the main by-products, thus enhancing the CO2 selectivity. This behaviour could be ascribed to the higher amount of hydroxyl radicals, which could boost the production of the direct precursors of CO2.

Two siblings affected with Cockayne syndrome (CS) are described: this diagnosis was suggested by the finding of a demyelinating neuropathy on electromyography in both children and consistent clinical features. CS is a rare genetic disorder with severe prognosis and a highly varied phenotype, making early diagnosis difficult. Taking into account these two cases and the literature, the current diagnosis criteria are insufficiently specific and appear late: the diagnosis may be delayed because multi-organ involvement and sensorial impairment suggests more frequent neurometabolic disorders. Neuroradiologic abnormalities are suggestive but may occur later. The finding of a demyelinating peripheral neuropathy seems to be a more useful marker to suspect this disorder in the presence of other clinical features. Further studies are required to better define the chronology of the symptoms, not only for adequate genetic counseling and eventual prenatal diagnosis, but also to assess the efficacy of future therapies.

The design of an alkali-surfactant-polymer (ASP) formulation for chemical Enhanced Oil Recovery poses multiple challenges from the experimental point of view. The present research examines the laboratory procedures and experimental results aimed at selecting the most suitable chemicals for an ASP pilot trial at the Caracara Sur field (Los Llanos Basin, Colombia). The key challenge was the limited compatibility of the surfactant and polymer selected under reservoir conditions (temperature and total salinity), leading to phase separation of the ASP solution and losses of the activity of both chemicals. An extension of the experimental program was required to re-design the formulation and mitigate risks of damaging the formation in the following field trials. The formulation comprised an alkyl benzene sulfonate as main ingredient, a hydrolyzed polyacrylamide as viscosifying agent and some weak alkali to reach the optimum salinity of the mixture. A mono-alkyl diphenyl disulfonate ether was added as coupling agent to improve compatibility of the ASP mixture. The performance of the selected ASP formulation was assessed by means of interfacial tension measurements, long-term thermal stability tests and dynamic core-flooding tests. The formulation provided ultra-low interfacial tension (< 10-2 mN/m) and viscosity enough to assure an appropriate mobility control. Hence, the formulation was considered to be suitable for further testing in the field pilot.

International audience; We retrospectively evaluated the role of rituximab (R) in maintenance treatment after autologous stem cell transplantationperformed in patients with relapsed follicular lymphoma. We compared the outcome of 67 follicular lymphoma (FL) patients according to the use of rituximab maintenance (RM) or not. All patients received rituximab plus chemotherapy before autologous stem-cell transplantation (ASCT). Patients received median of two lines of prior therapy. The RM schedule was one injection of rituximab every 3 months for 2 years. Median follow-up is 4.6 years. The 3-year progression-free survival (PFS) after ASCT was 86 % with RM vs. 46 % without (p = 0.0045). Median is not reached in the RM arm vs. 31 months in non-RM arm. The 3-year OS was 96 % with RM vs. 78 % without (p = 0.059). The present monocentric study shows that 2 years of RM after ASCT significantly increases response duration for non-naive rituximab relapsed FL patients compared with observation.

6th Central European Symposium on Plasma Chemistry (CESPC), Bressanone, ITALY, SEP 06-10, 2015; International audience; The propagation of a DC-pulsed argon plasma jet through the surrounding ambient air, and its interaction with an ungrounded glass plate placed on the jet trajectory, was studied by means of fast imaging. The surface plays an important role in the spatio-temporal characteristics of the plasma. Indeed, for an argon jet propagating perpendicularly to the surface, the plasma jet structure changes from filamentary to diffuse when the distance between the nozzle of the capillary tube and the surface is short (

6th Central European Symposium on Plasma Chemistry (CESPC), Bressanone, ITALY, SEP 06-10, 2015; The kinetics of four volatile organic compounds (VOCs) (propene, propane, acetaldehyde, acetone) were studied in plasmas of atmospheric gases using a photo-triggered discharge (homogeneous plasma) or a dielectric barrier discharge (filamentary plasma). It was shown for the homogeneous plasma that quenchings of nitrogen metastable states, A(3)Sigma(+)(u) and the group of singlets a `(1)Sigma(-)(u), a (1)Pi(g) and w(1)Delta(u), are important processes for the decomposition of such molecules. Recent measurements of the H-2 concentration produced in the N-2/C3H6 mixture emphasize that the hydrogen molecule can be an exit route for propene dissociation. It is also found that H-2 and CO molecules are efficiently produced following the dissociation of CH3COCH3 and the subsequent chemical reactivity induced by radicals coming from acetone. Addition of oxygen to a N-2/VOC mixture can change drastically the kinetics. However, the quenching processes of N-2 metastables by the VOC are always present and compete with oxidation reactions for the conversion of the pollutant. At low temperature, oxidations by O or by OH are not always sufficiently effective to induce an increase of the molecule decomposition when oxygen is added to the mixture. In particular, the presence of O-2 has a detrimental effect on the acetone removal. Also, as evidenced for acetaldehyde and propane, some kinetic analogies appear between filamentary and homogeneous plasmas.

Resume Une maladie de Lyme doit etre evoquee devant une paralysie faciale peripherique sans cause evidente chez un enfant en zone d’endemie, surtout si elle survient de mai a novembre, avec la notion d’un antecedent d’erytheme migrant, de piqure de tique ou d’exposition possible dans les semaines precedentes. La presentation clinique de cette borreliose differe sensiblement chez l’adulte et l’enfant et selon l’origine geographique de l’infection. Ces particularites rendent difficiles l’interpretation et l’application des diverses recommandations de prise en charge de cette maladie. Les neuroborrelioses sont plus frequentes en Europe qu’aux Etats-Unis et une meningite associee a la paralysie faciale est plus precoce et plus frequente dans la population pediatrique europeenne. Chez un enfant presentant une paralysie faciale peripherique dans un contexte faisant suspecter une maladie de Lyme, il parait donc necessaire de realiser une ponction lombaire afin d’etayer le diagnostic par une recherche de synthese intrathecale d’anticorps specifiques, parfois plus precoce que dans le serum, et d’adapter ainsi les modalites du traitement antibiotique. Une antibiotherapie par voie systemique est recommandee s’il existe des anomalies du liquide cephalo-rachidien, la voie orale etant reservee aux paralysies faciales isolees. Le suivi est clinique avec une collaboration indispensable entre le pediatre, l’infectiologue et l’oto-rhino-laryngologiste (ORL).

The removal of 500 ppm acetaldehyde in nitrogen at 1 bar is characterized in a pulse dielectric barrier discharge generating a spatial random distribution of plasma filaments. The identification and the quantification of numerous by-products are performed. At 20 °C, CH3CHO is efficiently dissociated, probably owing to quenching of N2 metastable states. The most abundant by-products are CO, H2, and CH4, in consistency with the three important exit channels for the quenching of the N2(A3Σ u + ) state by CH3CHO proposed by Faider et al. (2011). In order of importance, other products are HCN, C2H6, CH3CN, HNCO, CO2, CH3COCH3, C2H4, C2H5CN, NH3, C2H2, and a group of nitriles and of ketones. An increase of the temperature from 20 °C up to 300 °C induces a strong decrease of the removal characteristic energy, but the by-products types remain unchanged. Probably the reaction of H with CH3CHO plays a role in the removal of the molecule at 300 °C.

International audience; Treatment of relapse of hematological malignancies following allogeneic hematopoietic SCT (allo-HSCT) remains very challenging and relies usually on the readministration of chemotherapy combined with donor lymphocyte infusion (DLI). To enhance DLI effectiveness, lymphodepletion (LD) with fludarabine (Flu) and/or CY before the injection of lymphocytes is an attractive modality to modify the immune environment, leading possibly to suppression of regulatory T cells (T(reg)) and exposing the patient to cytokine activation. However, LD before DLI may lead to induction of deleterious GVHD. To avoid inducing overwhelming toxicity, we proceeded by escalating doses of both LD and DLI. Eighteen patients with various non-CML hematological malignancies who relapsed following allo-HSCT were treated with chemotherapy and LD-DLI or LD-DLI upfront. T-cell subpopulation and DC levels as well as cytokine plasma levels (IL-7, IL-15) were measured before and following LD-DLI. Cumulative incidence of acute grade II-IV GVHD was 29.4% similar to that reported in patients receiving DLI without LD. In addition, Flu alone with low dose of DLI was not associated with severe GHVD. CY/Flu at the respective doses of 600 mg/m(2) on day 1 and Flu 25 mg/m(2)/day on days 1-3 did not result in a marked decrease of T(reg) cells, nor in endogenous IL-7 and IL-15 production. However, a peripheral expansion of DCs was observed. These findings suggest that the escalated dose procedure appears safe and prevent overwhelming toxicity. A dose-limiting toxicity has not yet been reached.Bone Marrow Transplantation advance online publication, 28 November 2011; doi:10.1038/bmt.2011.231.

This single centre study assessed the incidence, kinetics and predictive factors of Epstein-Barr Virus (EBV) reactivation and EBV-related lymphoproliferative diseases (LPDs) in 175 consecutive patients who received a reduced-intensity conditioning (RIC) before allogeneic hematopoietic stem cell transplantation (allo-HSCT). The cumulative incidence of EBV reactivation at 6 months after allo-HSCT defined as an EBV PCR load above 1000 copies of EBV DNA/10(5) cells was 15%, and none of these patients experienced any sign or symptom of LPD. A total of 17 patients, who had EBV DNA levels exceeding 1000 copies/10(5) cells on two or more occasions, were pre-emptively treated with rituximab. With a median follow-up of 655 (range, 92-1542) days post allo-HSCT, there was no statistically significant difference in term of outcome between those patients who experienced an EBV reactivation and those who did not. In multivariate analysis, the use of antithymocyte globulin as part of the RIC regimen was the only independent risk factor associated with EBV reactivation (relative risk=4.9; 95% confidence interval, 1.1-21.0; P=0.03). We conclude that patients undergoing RIC allo-HSCT using anti-thymocyte globulin as part of the preparative regimen are at higher risk for EBV reactivation. However, this did not impact on outcome, as quantitative monitoring of EBV viral load by PCR and preemptive rituximab therapy allowed for significantly reducing the risk of EBV-related LPD.

Electron impact ionization of n -heptane was studied using mass spectrometry. Cross-sections for the formation of molecular ion and ionic fragments are measured between 10 eV and 86 eV with a total cross-section of 1.5 × 10 −16 cm 2 towards 50 eV. The molecular ion is the most abundant below 16 eV. The present results display good agreement between the measured total ionization cross-sections and the calculated one with the BEB model. Five ions C n H 2 n +1 + (2 ≤ n ≤ 6) result from a simple C–C bond split in the molecular ion. C 3 H 7 + , identified as isopropyl cation, is the most abundant of the ionic species above 16 eV. Four ions C n H 2 n + (2 ≤ n ≤ 5) result from a C–C bond split with H-atom rearrangement. C 3 H 6 + , identified as propene cation, is the most abundant of these four cations above 35 eV. Five other ions, C n H 2 n −1 + (2 ≤ n ≤ 4), cyclopropenyl and methyl cations may result from the ionization of C 4 H 9 , the major alkyl issued from the fragmentation of the molecular ion.

The products of 2-heptanone conversion by dielectric barrier discharge plasma are analyzed under different conditions: alternating current (ac) or pulsed mode of excitation, variable energy, variable composition of the carrier gas. The efficiency of the conversion is higher using a pulse excitation mode than an ac mode. With a small oxygen percentage (about 2-3%) added to nitrogen, 2-heptanone is about 30% more efficiently removed than in pure nitrogen, while the 2-heptanone removal decreases with an oxygen percentage higher than 3%. A new analysis method, based on chemical ionization mass spectrometry, is used for volatile organic compound detection along with chromatography. Several products issued from 2-heptanone conversion with ac excitation are identified in nitrogen and in air, and a chemical scheme is proposed to explain their formation and their treatment by the discharge. It appears that byproducts are issued not only from oxidation reactions, but also from C-C bond cleavage by collisions with electrons or nitrogen excited states.

Electron impact ionization of formaldehyde has been studied using mass spectrometry. Cross-sections for the formation of ions are measured between 10 and 85 eV with a total cross-section of 4 × 10 −16 cm 2 at 50 eV. H 2 CO + , HCO + and CO + contribute to about 99% of the total cross-section at 85 eV. The branching ratio for the formation of these cations is 0.32 (H 2 CO + ), 0.49 (HCO + ) and 0.19 (CO + ) between 45 eV and 85 eV. HCO + is the most abundant above 32 eV. Three other minor ions, O + , CH 2 + and CH + , are detected in the range 35–85 eV.

Toluene removal is investigated in filamentary plasmas produced in N2 and in N2/O2 mixtures by a pulse high voltage energised DBD. Influence of the oxygen percentage (lower than 10%) and of the temperature (lower than 350°C) is examined. Toluene is removed in N2 through collisions with electrons and nitrogen excited states. The removal efficiency is a few higher in N2/O2. It increases when the temperature increases for N2 and N2/O2. Both H- and O-atoms play an important role in toluene removal because H can readily recombine with O to form OH, which is much more reactive with toluene than O. H follows from dissociation of toluene and of hydrogenated by-products by electron collisions. Detection of cyanhidric acid, acetylene, formaldehyde, and methyl nitrate strengthens that dissociation processes, to produce H and CH3, must be taken into account in kinetic analysis. Formation and treatment of deposits are also analysed.

The electron impact ionization of acetone and 2-butanone between 10 and 86 eV has been studied using mass spectrometry. The cross-sections are measured for the formation of molecular ions and major fragment ions which are produced. The present results display good agreement between the measured total ionization cross-sections and the calculated with the BEB model. The enthalpies of formation and the ionization energies of several fragments are evaluated using ab initio calculations. For each ketone, the molecular ion and the 43 amu ion contribute to about 80% of the total cross-section at 86 eV. The 43 amu ion, identified as the acetyl cation, is the most abundant above 15 eV. Other ions present in the spectra of acetone are (i) the 42 amu ion, detected in the range 12–86 eV, contributes to about 6% of the total cross-section at the maximum voltage used and is identified at low energy as a ketene cation, (ii) six other minor ions (39, 27, 26, 44, 29 and 15 amu) were detected above 17 eV. Five of them may result from dissociation reactions of the molecular ion while the methyl cation is issued from the 43 amu ion. In the spectra of 2-butanone, other ions are (i) the 57 amu ion detected in the range 11–86 eV and identified as the propionyl cation, contributes to about 6% of the total cross-section over the whole ionization energy range, (ii) four other minor ions (42, 29, 27 and 15 amu) were detected above 18 eV and there formation is similar to that of acetone. Effects of fragment size favour from the molecular ion, the formation of the 57 amu ion near the threshold, and at higher energy, the formation of the 43 amu ion.

De plus en plus de patients survivent maintenant a long terme, apres une greffe de cellules souches hematopoietiques allogeniques et autologues. L’etude des effets a long terme apres greffe, constitue donc actuellement un aspect majeur de la prise en charge de ces patients. Deux types de complications sont a decrire: les complications malignes (cancereuses) et les complications non malignes.

A photo-triggered discharge is used to study the influence of three hydrocarbons (HCs), propene (C3H6), n-decane (C10H22), and toluene (C6H5CH3) on NO conversion in N2/O2/NO/HC mixtures, with 18.5% O2 concentration, 700 ppm of NO, and an hydrocarbon concentration ranging between 190 ppm and 2,700 ppm. The electrical system generates a transient homogeneous plasma, working under 400 mbar total pressure, with a 50 ns short current pulse at a repetition frequency up to a few Hz. The NO concentration at the exit of the reactor is quantified using absolute FTIR spectroscopy measurements, as a function of the specific deposited energy in the discharge and the mixture composition. Owing to the plasma homogeneity, the experimental results can be compared to predictions of a self-consistent 0-D discharge and kinetic model based on available data in the literature about reactions and their rate constants. It is shown that the addition of either propene (as for DBD or corona discharges) or n-decane to N2/O2/NO leads to an improvement of the NO removal as compared to the mixture without hydrocarbon molecules. The adopted kinetic schemes explain this effect for the two mixture types. On the other hand, both the experiments and model predictions emphasize that the addition of toluene does not lead to the improvement of NO conversion. Moreover, compounds that are useful for NOx reduction catalysis, such as aldehydes, are less produced in the mixture with toluene.

A photo-triggered discharge has been used to study the production kinetic mechanisms and the reactivity of the hydroxyl radical in a N2/O2 mixture (5% oxygen) containing ethane or ethene for hydrocarbon concentration values in the range 1000?5000?ppm, at 460?mbar total pressure. The discharge (current pulse duration of 60?ns) has allowed the generation of a transient homogeneous non-equilibrium plasma, and the time evolution of the OH density has been measured (relative value) in the afterglow (up to 200??s) by laser induced fluorescence (LIF). Experimental results have been explained using predictions of a self-consistent 0D discharge and plasma reactivity modelling, and reduced kinetic schemes for OH have been validated. It has been shown that recombination of H- and O-atoms, as well as reaction of O with the hydroperoxy radical HO2, plays a very important role in the production of OH radicals in the mixture with ethane. H is a key species for production of OH and HO2 radicals. As for ethane, O, H and HO2 are key species for the production of OH in the case of ethene, but carbonated radicals, following the partial oxidation of the hydrocarbon molecule by O, also play a non-negligible role. The rate constant for O- and H-atom recombination has been estimated to be 3 ? 10?30?cm6?s?1 at near ambient temperature, consistent with LIF measurements on OH for both mixtures with ethane and ethene.

Electron impact ionization of toluene is studied using mass spectrometry. Cross-sections for the formation of molecular ions and ionic fragments are measured between 10 and 78 eV with a total cross-section of 1.5 × 10 - 15 cm 2 towards 60 eV. C 7 H 8 + and C 7 H 7 + contribute to 75% of the total cross-section at 78 eV. The molecular ion is the most abundant below 25 eV. Four ionic fragments: C 5 H 5 + , C 4 H 3 + , C 5 H 3 + and C 3 H 3 + , are detected above 20 eV. Enthalpy considerations can lead to think that C 5 H 5 + is issued directly from the molecular ion, whereas the three other species result from two step pathways.

Abstract 4045 Lenalidomide is an effective and widely used therapeutic agent for multiple myeloma. This agent exhibits both anti-tumor and immunomodulatory properties. Recent data suggested a positive impact on outcome of this drug in the setting of maintenance therapy in young multiple myeloma patients receiving autologous stem cell transplantation. On the long term, Lenalidomide is thought to enhance activation of T and NK cells, however its precise immune effects remain to be elucidated, and only a few data is available in this field. This single centre pilot prospective study aimed to assess T-cell polarization and the cytokine secretion profile in ten patients treated with lenalidomide alone in the maintenance setting. In this cohort, patients received at time of analysis between 4 and 12 cycles of lenalidomide alone (one cycle=28 days) at a dose ranging between 5 and 15 mg/day. Five patients received prior high-dose therapy (HDT) and autologous peripheral blood stem cell transplant (PBSCT) and 5 patients received maintenance after induction with the VRD (lenalidomide, bortezomib and dexamethasone) combination. Seven patients were in very good partial response (VGPR) and 3 were in complete response (CR) at the time of analysis. Intracellular cytokine secretion by peripheral blood lymphocytes was analyzed in peripheral blood mononuclear cells (PBMC) by multicolour staining. PBMCs were stimulated for 5 hours with PMA and ionomycin in the presence of 10 μg/mL Brefeldin A. Cells were first stained with CD3 APC-H7, CD4 PE-Cy7 and CD8 APC and permeabilized using Cytofix/cytoperm and were then incubated with FITC-, PE-, PeCy7, V450 Horizon-, AlexaFluor 647- conjugated anti-IFN-gamma, IL-4, IL-10, IL-17A and IL-21. In parallel, we analyzed a total of 39 cytokines in the plasma collected simultaneously from these same patients. Concentrations of IL-21, IL-23, TARC (CCL17), TRAIL (Apo2L), CD40L, Flt3L, Fractalkine (CX3CL1), IFNalpha, IFN-gamma, IL-10, IL-12p40, IL-12p70, IL-13, IL-15, IL-17, IL-1a, IL-1b, IL-1Ralpha, IL-2, IL-2Ralpha, IL-3, IL-4, IL-5, IL-6, IL-7, IL-8 (CXCL8), IL-9, IP10 (CXCL10), MCP-1 (CCL2), MCP-3(CCL17), MIP-1alpha (CCL3), MDC (CCL22), MIP-1beta (CCL4), TGFalpha, TNFalpha, TNFbeta, VEGF, Eotaxin and EGF were determined by the bead-based multiplex protein array technology. We observed that T cells derived from myeloma patients receiving lenalidomide maintenance therapy exhibited a significantly higher secretion of TNF-alpha (p=0.03), IL-4 (p=0.003), IL-10 and IL-21 (p=0.004), compared to stimulated T cells obtained from 5 healthy donors (Figure 1 A-B). In the multiplex bead assay, we observed that IP10 (p=0.008), IL-8 (p=0.018), and MIP1beta (p=0.022) levels were also statistically increased in the plasma of patients treated with lenalidomide compared to the control group (Figure 2). Overall, these results suggest that the use of lenalidomide as maintenance therapy in myeloma can induce some potent and critical immunostimulatory activities through induction of a chronic inflammatory reaction. Interestingly, IP10 is a major Th1-related chemokine involved in anti-tumor responses, while IL-8 and MIP1b can positively influence NK cell functions (maturation, migration and augmenting their cytolytic activity). Altogether, these data shed some new light on the immunostimulatory mechanism of action of lenalidomide in the setting of long term maintenance therapy for myeloma, highlighting the need for detailed immunomonitoring studies to be performed as part of the large multicentre randomized trials. Disclosures: No relevant conflicts of interest to declare.

Chemical Enhanced Oil Recovery (CEOR) in a multi-layered reservoir environment with moderate to strong natural water-drive is a complex process with associated risks and uncertainties. Reservoir simulation is one of the most important tools available to predict behavior under chemical flooding conditions and to study sensitivities aimed to a cost-effective CEOR process implementation. Key to the success of a reliable reservoir simulation is the application of a de-risking process and the acquisition of important calibration data, such as laboratory core-flood data and field-scale pilot experiments. A CEOR pilot is currently undertaken in the Caracara Sur (CCS) field (Llanos Basin, Colombia) which has an unfavorable mobility ratio and very low water salinity. However challenges exist, such as strong water drive (no water injection experience), high temperature and a complex geological nature (up to 15 reservoir layers that made up of multiple isolated distributary channels). A detailed reservoir simulation model was built to study full field implementation of CEOR in Caracara Sur. The model was calibrated with laboratory tests data, residual oil saturations from Single Well CEOR ASP Well Tracer Test Pilots, injectivity tests and breakthrough times from inter-well tracer tests. The paper discusses the approaches taken for full field modeling of Caracara Sur using commercial software and describes how the data collected from alkaline/surfactant/polymer (ASP) core flooding were up scaled and used in pilot sector modeling and for designing tracer back flow tests (TBFT) and single well tracer tests (SWTT) before and after ASP flooding. The TBFT and SWTT results in a pilot injection well, in the middle of three producers, confirmed the absence of aquifer drift, which was also predicted by pilot sector modeling. The paper explains how the obtained results from the tracer tests (residual oil saturations, breakthrough times) and well injectivity were used to calibrate the full field numerical model for reliable prediction of the effectiveness of the ASP flooding.

To ensure a technically and economically viable chemical Enhanced Oil Recovery (cEOR) project in the Caracara Sur Field (Llanos Basin Colombia), several challenges were faced. One of the challenges described in a previous work (Cubillos et al. 2013), is the design of an efficient chemical formulation stable at reservoir conditions. Comprehensive laboratory work has been undertaken, resulting in an Alcali Surfactant Polymer (ASP) formulation containing hydrolysed polyacrylamide (HPAM) as a mobility control agent. HPAM is the most used polymer in the oil industry thanks to its low cost and availability in high quantities. However, initially it was not clear that HPAM efficiently worked for Caracara Sur, because HPAM properties limits its efficient application to low temperatures ( In this paper, we present the laboratory work that lead to find an innovative solution founded on the synergy between the formation water properties (low salinity) and high temperature environment in the Caracara Sur Field. The study focused on the polymer screening process, rheological properties of HPAM with the low salinity brine of Caracara Sur, the HPAM performance in porous media and chemicals to enhance its thermal stability. This work is only focused on the polymer selection and the synergy between low salinity brine and polymer flooding. The main results show that the developed formulation for the Caracara Sur reservoirs is a viable cEOR alternative. By injecting low salinity brine and HPAM with the right mix of other chemical components, it is possible to drastically reduce the cost of cEOR, whilst maintaining the same efficiency even at higher reservoir temperature. As a final product, an optimal ASP formulation has been developed and successfully tested both at laboratory and field conditions.

Electron impact ionisation of 2-propanol and ethanal is studied using mass spectrometry. Cross-sections of the formation of molecular ions and ionic fragments are measured between 14 and 86 eV. Free energy changes are evaluated using ab initio calculations. For 2-propanol, two ions, identified as CH 3 CHOH + (45 amu) and CH 3 CHCH 3 + (43 amu), contribute more than 75% to the total cross-section over the whole range of electron energies and are produced by simple bond cleavage in the molecular ion. Both processes occur spontaneously, leaving the molecular ion as a minority species. For ethanal, two ions, identified as HCO + (29 amu) and CH 3 CO + (43 amu), and the molecular ion (44 amu) contribute more than 80% to the total cross-section. The ions of 29 and 43 amu result from a simple bond cleavage in the molecular ion. These sprocesses are not spontaneous and the contribution of the molecular ion becomes predominant at 15 eV and is therefore significant over the whole range of ionisation energies.

2-heptanone is representative of a class of odorous molecules. Recent studies have shown that by adding a catalyst to a dielectric barrier discharge (DBD) plasma, the elimination of 90% of this molecule can be achieved with low consumption of electric energy, at room temperature, for concentrations below 1000 ppm. In the presented work, the removal of the ketone by OBD, both in dry air and within a slice of a honeycomb monolith of cordierite without a catalyst, was studied. In both experiments, the discharge was operated in a plane-to-plane geometry with a discharge volume of 10 cm 3 . A high voltage, bipolar pulse generator (40 kV max, 1-140 Hz freauency range) was used, In dry air, it was found that 2-heptanone is almost totally removed (>95%) for a specific deposited energy of about 500 J . l - 1 , but this elimination is less effective in the porous cordierite reactor (80%) for the same energy. This effect is explained by the very different spatial distribution of the plasma within the discharge volume, as seen using a CCD camera. Moreover, the adsorption-desorption equilibrium of the molecule at the surface of the material is greatly influenced by the discharge.

The electron impact ionisation of 2-heptanone between 13 and 78 eV is studied using mass spectrometry. CH3C(O)CH2CH2CH2CH2CH3+ and fragment ions are produced with a total cross-section of 5 × 10−16 cm2 towards 50 eV. Two ions, identified as CH3CO+ (43 amu) and CH3C(OH)CH2+ (58 amu), contribute to about 60% of the total cross-section for electron energies above the ionisation threshold. The detected ions are identified using ab initio calculations. For E = 14 eV, the ion of 58 amu is the most abundant followed by an ion of 59 amu identified as being CH3C(OH)CH3+; they result from a bond cleavage with one or two H atom rearrangements. For E ≥ 48 eV, the ion of 43 amu is the most abundant; it results from an α-cleavage reaction in the molecular ion.

A plasma-catalyst reactor was used to eliminate a low concentration (180 ppm) of 2-heptanone in air by total oxidation. This VOC is representative of a class of odorous ketones. A DBD-type plasma was generated through a platinum-based catalyst supported on an alumina wash-coated honeycomb monolith by means of a high voltage bi-polar pulsed excitation. The 2-heptanone elimination efficiency increases with the energy density. More than 97% of 2-heptanone conversion is observed, in dry air condition for an energy density of 200 J/L. An important synergy effect has been observed between cold plasma and catalyst, the 2-heptanone conversion remaining less than 50% on an uncoated monolith, even at an energy density value higher than 500 J/L. The presence of water (3 mol%) in the gas phase, slightly decreases the efficiency of the 2-heptanone elimination, but strongly decreases the ozone formation in the 100–300 J/L energy density range.

Experimental investigations and kinetic interpretation indicate the presence of several peroxidic species during the oxidation of n-dodecane. The oxidation was performed either in the gaseous phase in a flow system, or with a liquid/gas interaction in a bulb, because in many combustion processes liquid and gas coexist during preignition. The different peroxides were identified by mass spectrometry. Simple hydroperoxides with two oxygen atoms per molecule were observed at relatively low temperatures above 370 K with liquid and gas present. Ketohydroperoxides with three oxygen atoms per molecules are formed at ∼500 K. Di-, and even tri-, ketohydroperoxides with four or five oxygen atoms per molecule are also present under these experimental conditions at 518 K. Their formation is explained by isomerization reactions of alkoxy radicals OR −2H O bearing a carbonyl group; these stem from the decomposition of carbonyl-hydroperoxides. Depending on the experimental conditions, the nature of the hydroperoxides is different and the respective reactions of these species should be introduced in low temperature oxidation mechanisms. These reaction schemes should include the isomerization of peroxy radicals RO 2 and of ketoalkoxy radicals OR −2H O, leading to the formation of peroxides with several carbonyl groups.

Engine and laboratory experiments are performed to understand the formation of deposits during ignition delay. An experimental Diesel engine allows to observe deposit formation as a global phenomenon including homogeneous and heterogeneous reactions as well as interaction between liquid and gaseous phases. A CFR engine is used to work under the same global conditions but without the liquid phase. A flow reactor enables to investigate the effects of defined and controlled temperatures and fuel/air ratios. Results show that deposit formation is facilitated by temperatures of the oxidized gases within the 290 - 350°C range and by the presence of the liquid phase. In this temperature range, carbo-nyl-hydroperoxides ORO2H, RO and RO2 radicals are known to be present and to play an important role. Various species are identified (carboxylic acids, aldehydes, ketones, dione, furanone) by GC/MS. Homogeneous and heterogeneous reactions of RO and RO2 radicals yield analogous types of compounds. All these results all...