Tuning the dynamics of imidazolium-based ionic liquids via hydrogen bonding. I. The viscous regime.

Combining results from impedance spectroscopy and oscillatory shear rheology, the present work focuses on the relation between the mass and charge flows and on how these are affected by the H-bonding in viscous ionic liquids (ILs). In particular, we compare the relaxational behaviors of the paradigmatic IL 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI) and its OH-functionalized counterpart 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (OHEMIM-TFSI). Our results and their analysis demonstrate that the presence of cationic OH-groups bears a strong impact on the overall dynamics of OHEMIM-TFSI, although no signatures of suprastructural relaxation modes could be identified in their dielectric and mechanical responses. To check whether at the origin of this strong variation is the H-bonding or merely the difference between the corresponding cation sizes (controlling both the hydrodynamic volume and the inter-charge distance), the present study includes 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (PMIM-TFSI), mixtures of EMIM-TFSI and PMIM-TFSI with lithium bis(trifluoromethylsulfonyl)imide (Li-TFSI), and mixtures of OHEMIM-TFSI with PMIM-TFSI. Their investigation clearly reveals that the dynamical changes induced by H-bonding are significantly larger than those that can be attributed to the change in the ion size. Moreover, in the mixtures of OHEMIM-TFSI with PMIM-TFSI, a dilution of the OH-groups leads to strong deviations from ideal mixing behavior, thus highlighting the common phenomenological ground of hydroxy-functionalized ILs and other H-bonded liquids.

Mixing Enthalpy for Binary Mixtures Containing Ionic Liquids.

A complete review of the published data on the mixing enthalpies of mixtures containing ionic liquids, measured directly using calorimetric techniques, is presented in this paper. The field of ionic liquids is very active and a number of research groups in the world are dealing with different applications of these fluids in the fields of chemistry, chemical engineering, energy, gas storage and separation or materials science. In all these fields, the knowledge of the energetics of mixing is capital both to understand the interactions between these fluids and the different substrates and also to establish the energy and environmental cost of possible applications. Due to the relative novelty of the field, the published data is sometimes controversial and recent reviews are fragmentary and do not represent a set of reliable data. This fact can be attributed to different reasons: (i) difficulties in controlling the purity and stability of the ionic liquid samples; (ii) availability of accurate experimental techniques, appropriate for the measurement of viscous, charged, complex fluids; and (iii) choice of an appropriate clear thermodynamic formalism to be used by an interdisciplinary scientific community. In this paper, we address all these points and propose a critical review of the published data, advise on the most appropriate apparatus and experimental procedure to measure this type of physical-chemical data in ionic liquids as well as the way to treat the information obtained by an appropriate thermodynamic formalism.

How is charge transport different in ionic liquids? The effect of high pressure.

Modern ionic liquids (ILs) are considered green solvents for the future applications due to their inherited advantages and remarkable transport properties. One of the ubiquitous properties of ILs is their intrinsic ionic conductivity. However, understanding of the super-Arrhenius behavior of the ionic conductivity process at elevated pressure still remains elusive and crucial in glass science. In this work, we investigate the ion transport properties of 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide: [C4mim][NTf2], 1-butylimidazolium bis[(trifluoromethyl)-sulfonyl]imide: [C4Him][NTf2] and 1-butylimidazolium hydrogen sulfate: [C4Him][HSO4] ILs in the supercooled liquid state using dielectric spectroscopy at ambient and high pressure. We present the experimental data in the dynamic window of the conductivity formalism to examine the charge transport properties. The frequency-dependent ionic conductivity data have been analyzed using the time-temperature superposition principle. In the Arrhenius diagram, the thermal evolution of the dc-conductivity reveals similar temperature dependence for both protic and aprotic ILs thus making it difficult to distinguish the ion dynamics. However, our results demonstrate the key role of high pressure that unambiguously separates the charge transport properties of protic ILs from aprotic ones through the apparent activation volume parameter. We also highlight that the activation volume can be employed to assess the information connecting the ability of ionic systems to form H-bond networks and the impact of proton transfer involved in the conduction process.

On the scaling behavior of electric conductivity in [C4mim][NTf2].

In this work we examine, for the first time, the molar conductivity behavior of the deeply supercooled room temperature ionic liquid [C4mim][NTf2] in the temperature, pressure and volume thermodynamic space in terms of density scaling (TV(γ))(-1) combined with the equation of state (EOS). The exponent γσ determined from the Avramov model analysis is compared with the coefficient obtained from the viscosity studies carried out at moderate temperatures. Therefore, the experimental results presented herein provide the answer to the long-standing question regarding the validity of thermodynamic scaling of ionic liquids over a wide temperature range, i.e. from the normal liquid state to the glass transition point. Finally, we investigate the relationship between the dynamic and thermodynamic properties of [C4mim][NTf2] represented by scaling exponent γ and Grüneisen constant γG, respectively.

Long-range and targeted ectopic recombination between the two homeologous chromosomes 11 and 12 in Oryza species.

Whole genome duplication (WGD) and subsequent evolution of gene pairs have been shown to have shaped the present day genomes of most, if not all, plants and to have played an essential role in the evolution of many eukaryotic genomes. Analysis of the rice (Oryza sativa ssp. japonica) genome sequence suggested an ancestral WGD ∼50-70 Ma common to all cereals and a segmental duplication between chromosomes 11 and 12 as recently as 5 Ma. More recent studies based on coding sequences have demonstrated that gene conversion is responsible for the high sequence conservation which suggested such a recent duplication. We previously showed that gene conversion has been a recurrent process throughout the Oryza genus and in closely related species and that orthologous duplicated regions are also highly conserved in other cereal genomes. We have extended these studies to compare megabase regions of genomic (coding and noncoding) sequences between two cultivated (O. sativa, Oryza glaberrima) and one wild (Oryza brachyantha) rice species using a novel approach of topological incongruency. The high levels of intraspecies conservation of both gene and nongene sequences, particularly in O. brachyantha, indicate long-range conversion events less than 4 Ma in all three species. These observations demonstrate megabase-scale conversion initiated within a highly rearranged region located at ∼2.1 Mb from the chromosome termini and emphasize the importance of gene conversion in cereal genome evolution.

Impact of radiotherapy on survival in resected or unresectable anaplastic thyroid carcinomas, a Rare Cancer Network study.

PURPOSE: Anaplastic thyroid carcinomas (ATC) are a heterogenous group of tumors of overall dismal prognosis. We designed models to identify relevant prognostic factors of survival of irradiated ATC patients including radiotherapy modalities (field size, dose). MATERIAL AND METHODS: Between 2000 and 2017, 166 ATC patients' treatments were divided into surgery and postoperative radiotherapy (poRT) or definitive radiotherapy (RT). Multiple imputation approach was used for missing data. Prognostic factors were identified using Lasso-penalized Cox modelling and predicted risk scores were built. RESULTS: Patients undergoing RT (n=70) had more adverse patient and disease characteristics than those undergoing poRT (n=96). Corresponding median survival rates were 5.4 and 12.1 months, respectively. PoRT patients undergoing poRT more likely received extended-field radiotherapy with prophylactic nodal irradiation, but rather received platinum- vs. adriamycin-based chemoradiotherapy. Radiotherapy was conventionally fractionated, delivered >60Gy in 51.9% and 61.7% and used extended fields in 88.5% and 71.2% of patients with poRT or RT. Radiotherapy interruption rates for toxicity were similar in the two groups. The best poRT-group model identified age>45yo, PS≥1, pathologic tumor stage≥pT4b,>N1 and R2 resection as poor prognostic factors. The best RT-group model (C-index of 0.72) identified PS≥3,>N1 and extended-field radiotherapy with prophylactic nodal irradiation (as opposed to tumour-bed irradiation only) as poor prognostic factors. CONCLUSION: In patients undergoing poRT, radiotherapy parameters had little influence over their survival irrespective of patient, disease characteristics, and quality of resection. In patients undergoing RT, extended-field radiotherapy improved survival in addition to PS and nodal stage.

Efficacy and safety of hypofractionated stereotactic radiotherapy for brain metastases using three fractions: A single-centre retrospective study.

PURPOSE: Hypofractionated stereotactic radiotherapy (HFSRT) has become a standard of care for patients with a limited number of brain metastases (BM). An increasing number of linear accelerators (LA) are able to accurately perform HFSRT including VersaHD® (Elekta®) LA. The main aim of this study was to report clinical outcomes of BM treated by HFSRT using 3×7.7Gy on 70% isodose line in terms of local control (LC). PATIENTS AND METHODS: Between November 2016 and October 2018, all patients suffering from histologically-proven primary with one or several newly diagnosed BM treated by HFSRT were retrospectively included and evaluated. Patients who had received prior treatment by neurosurgery or cerebral radiotherapy were excluded. RESULTS: Among 44 patients, 61 BM were treated. With a median follow-up of 31.9 months, LC rates at 6 and 12 months were 93.2% and 90.9, respectively. Single-BM was independently predictive of LC (P=0.025) and overall survival (P=0.013). Acute toxicity rates were acceptable: 65.9% of patients had grade 1 and 2 and no acute grade 3 toxicity according to the NCI-CTCAE (version 5.0). Regarding delayed toxicity, one case (2.3%) of radionecrosis was confirmed by magnetic resonance spectroscopy. CONCLUSION: In our single-centre retrospective analysis, BM treatment by HFSRT delivered in three fractions showed a 12-month LC rate of 90.9% without major toxicities, which suggests safety and efficiency of this technique. However, longer-term follow-up and prospective studies are still needed to confirm these results.

A TY1 element is inserted in the CYR1 control region of Saccharomyces cerevisiae strain AB320.

Southern blotting using a 5'-proximal probe of the Saccharomyces cerevisiae CYR1 gene has revealed heterogeneity in laboratory strains. It is demonstrated that strain AB320 contains a Ty1 element inserted in the promoter region of CYR1. The Ty1 orientation suggests that transcription of CYR1 is initiated downstream from the insertion region.

The effects of subcurative doses of chloroquine on Plasmodium vinckei petteri gametocytes and on their infectivity to mosquitoes.

The effects of subcurative doses of chloroquine on rodent and human Plasmodium transmission to the mosquito have been studied by several authors who showed a short-term (12 h) enhancement of gametocyte infectivity by the drug, restricted to chloroquine-resistant strains, and a long term (4-6 days) enhancement of gametocytogenesis of chloroquine-sensitive strains of Plasmodium chabaudi. We investigated both short- and long-term effects of chloroquine on Plasmodium vinckei petteri, a chloroquine-sensitive rodent Plasmodium strain. Chloroquine treatment reduced the index of gametocytogenesis to 73% (5 mg/kg) and 55% (2.5 mg/kg) of controls, on day 6 post-infection (p.i.). The reduction was statistically significant with 5 mg/kg chloroquine. However, the reduction of gametocyte numbers did not affect the transmission capabilities of the strain. Our experiments showed that doses of 1 mg/kg chloroquine had no effect on the oocyst counts, 12 h post-administration to mice. A statistically non-significant 61% reduction of oocyst numbers was observed in mosquitoes fed on mice treated with 5 mg/kg chloroquine. The effect of 5 mg/kg chloroquine administration on the infectivity of gametocytes to mosquitoes fed 1 h post-treatment was also investigated. An overall 41% reduction of oocyst numbers was observed. This immediate effect was statistically significant in 73% of the mice. These results are consistent with the hypothesis that the short-term enhancing effect of chloroquine on transmission is restricted to the drug-resistant strains of Plasmodium.

Quantitative trait loci for resistance against Yellow rust in two wheat-derived recombinant inbred line populations.

Yellow rust, which is a major disease in areas where cool temperatures prevail, can strongly influence grain yield. To control this disease, breeders have extensively used major specific resistance genes. Unfortunately this kind of resistance is rapidly lost due to pathogen adaptation. More-durable resistance against yellow rust can be achieved using quantitative resistance derived from cultivars with well-established durable resistance. The winter wheat Camp Remy has maintained a high level of resistance for over 20 years. In order to map quantitative trait loci (QTLs) for durable yellow rust resistance, we analysed a set of 98 F(8) recombinant inbred (RI) lines derived from the cross Camp RemyxMichigan Amber. We also mapped QTLs for adult resistance to yellow rust using the International Triticae Mapping Initiative RI population (114 lines derived from the cross Opata85xsynthetic hexaploid). Two and five QTLs, respectively, were identified from these two populations. This work has highlighted the importance of the centromeric region of chromosome 2B and the telomeric regions of chromosomes 2AL and 7DS in durable yellow rust resistance. The same chromosomal regions are also implicated in resistance to other pathogens.

A Candida albicans metallopeptidase degrades constitutive proteins of extracellular matrix.

Among potential virulence factors of Candida albicans, enzymes seem to play an important role. Many studies concern the secreted aspartic proteinases (saps), and the degradation of some components of the subendothelial extracellular matrix by the isoenzyme sap2 has been proved. Nevertheless, other proteolytic enzymes could be involved in the pathogenicity of the yeast. We studied the degradation of four constitutive proteins of the extracellular matrix: type I and IV collagens, laminin and fibronectin, by a 95-kDa metallopeptidase, localised in the cell wall of C. albicans. Each of these constituents was incubated with the purified enzyme and its degradation products analysed by an electrophoretic method. We observed that type I collagen and fibronectin were totally degraded by the enzyme whereas type IV collagen and laminin were only partially degraded. The C. albicans metallopeptidase may play a role in the degradation of the subendothelial extracellular matrix components. This enzyme could facilitate the migration of the yeast in the tissues after crossing the endothelial layer, allowing the fungal invasion of target organs.

Purification and characterisation of a metallopeptidase of Candida albicans.

A novel aminopeptidase was purified by high performance liquid chromatography from a cytosoluble 100,000 g extract of Candida albicans on the basis of its ability to cleave L-arginine 7-amino-4-methylcoumarin. The purification factor was 36 and the yield was 20%. The native enzyme had a mol. wt of 52 kDa as demonstrated by SDS-PAGE in the presence or absence of reducing conditions and exhibited an iso-electric point of 4.3. The aminopeptidase showed optimum activity at pH 7.2, a Michaelis constant of c. 50 microM and a Vmax at 19 mM AMC released/min/mg of protein for L-Arg-AMC. This enzyme was shown to cleave at low affinity L-leucine-7-amino-4-methylcoumarin as demonstrated by the spectrofluorimetric method. The enzyme was strongly inhibited by specific metallo-enzyme inhibitors-EDTA and o-phenanthroline. Furthermore, there is evidence that a similar or identical enzyme occurs in other C. albicans clinical isolates and other Candida spp.

Imported Plasmodium vivax malaria in France: geographical origin and report of an atypical case acquired in Central or Western Africa.

A total of 73 cases of Plasmodium vivax infections acquired in Western or Central Africa were diagnosed on microscopical criteria in French travellers from 1995 to 1998. We report a case of P. vivax infection in a non immune traveller confirmed by polymerase chain reaction and presenting an atypical P. ovale morphology. The infection was acquired in Western or Central Africa. These microscopical observations, together with the molecular evidence for P. vivax in Western and Central Africa suggest that P. vivax is transmitted in this area despite lacking the Duffy receptor in autochthonous population.

Seroprevalences of Toxoplasma, malaria, rubella, cytomegalovirus, HIV and treponemal infections among pregnant women in Cotonou, Republic of Benin.

Seroprevalences for toxoplasmosis, malaria, rubella, cytomegalovirus, HIV and treponemal infections were evaluated among 211 pregnant women residing in the Cotonou area, Republic of Benin. One hundred and thirteen women (53.6%) had toxoplasma antibodies, 185 (87.7%) malaria antibodies and 181 (85.8%) rubella antibodies. Among the 205 (97.2%) women with cytomegalovirus antibodies, 6 presented recent or current infection. No HIV seropositivity was detected. Five (2.4%) of these women had a positive treponematosis serology corresponding to previous infection or reinfection. These results were compared with previous studies conducted in Africa. Routine serological screening should be recommended in young age and in pregnancy for rubella, only in pregnant women for HIV and toxoplasma infections, in order to control their possible consequences on women and newborns.

Secondary failure of islets autotransplantation in totally pancreatectomized dogs: a multifactorial study.

Even without any immunologic barrier, as in autografts, reversal of diabetes induced by islets transplantation is not definitive and a secondary failure generally occurs. Factors involved in this failure were investigated in 13 male dogs undergoing total pancreatectomy and extemporaneous islets reinjection in the portal circulation. Five dogs died from postoperatory complications, three remained diabetic, and five were normoglycemic without insulin therapy for a duration of two to 26 weeks. Factors associated with failure appeared to be: (a) hemorrhage during dissection of pancreas prior to islets isolation, (b) imperfect collagenase digestion. Moreover, duration of this period of normoglycemia was negatively correlated with glycemia on the 20th postoperatory hour (r = 0.759, p less than 0.05), suggesting a possible relationship between glycemia and further graft outcome. Therefore, such a multifactorial statistical analysis seems to be helpful for the study of multiple technical parameters associated with the prognosis of islets transplantations.

Immunoreactive somatomedin C in children from Morocco: a biological marker of nutritional growth retardation?

Somatomedin C (Sm-C) is supposed to be a sensitive marker of malnutrition. Its relationship to growth and protein intake was investigated in 47 Moroccan children. The children (mean age: 7.5 +/- 2 yr) had no endocrine abnormality. Anthropometric parameters were measured, together with blood levels of Sm-C and growth hormone (GH). Lower values of Sm-C were found in the following situations: (a) growth retardation (more than -2 Sd, N = 23; Sm-C = 3.61 +/- 0.42 nmol/l vs. 13.38 +/- 1.52, P less than 0.02); (b) body weight less than 80% of expected weight for height (N = 8; Sm-C = 4.84 +/- 0.97 vs. 10.33 +/- 1.19, P less than 0.02); (c) boys with meat consumption less than 3 times per wk (N = 15; Sm-C = 4.03 +/- 0.71 vs. 12.35 +/- 2.01, P less than 0.002). Thus, lower values of Sm-C are found in association with weight insufficiency and lower protein intake. As has previously been assumed, serum Sm-C, which is regulated by nutrition, may be a sensitive tool in the assessment of nutritional status in developing countries such as Morocco. Furthermore, it could explain some cases of growth retardation in states of malnutrition.

[Comparison of two techniques for detection of anti-Plasmodium falciparum antibodies: Falciparum-spot IF (Biomérieux) and Malaria IgG Celisa (BMD). Preliminary results]. / Comparaison de deux techniques de détection des anticorps anti-Plasmodium falciparum: Falciparum-spot IF (Biomérieux) et Malaria IgG Celisa (BMD). Résultats préliminaires.

We compared a new Elisa assay to detect malaria antibodies: Malaria IgG Celisa (BMD) with the IFAT technique Falciparum-spot IF (Biomérieux): sensitivity, specificity, predictive positive and negative values were 81%, 99%, 95%, 95%, respectively. Eight patients had positive thick blood smear out of 23 performed. For these eight confirmed acute malaria cases, the Elisa assay was negative in five instances. For two recent malaria attacks both Elisa and IFI were negative. With blood donors, two sera were IFAT positive and Elisa negative; 16 were IFAT doubtful and Elisa negative. Doubtful results rose up to 13.5% by IFAT against 1.5% by Elisa assay. We preferred kappa coefficient instead of chi 2 test for data analysis, which measures the concordance degree between the two techniques. Here concordance is moderate. Choosing an Elisa assay to detect the transmission of malaria for at-risk blood donors collides with the method sensitivity compared with IFAT as reference.

[Critical study of ELISA technique and high sensitivity direct agglutination test for the screening of antitoxoplasma IgG]. / Etude critique d'une technique ELISA et d'un test d'agglutination directe haute sensibilité pour le dépistage des IgG antitoxoplasmiques.

The authors have evaluated an ELISA (Toxo-IgG EIA; bioMérieux) and a direct agglutination test using a sensitized antigen (Toxo-Screen DA; bioMérieux), with a fluorescent test antibody (Toxo-Spot IF; bioMérieux) as a reference for the screening of toxoplasmosis IgG antibodies. A good correlation was obtained for these two methods with fluorescent test antibody (p less than 0.00001) on 841 sera. However, results obtained with direct agglutination test were better than those obtained with ELISA (direct agglutination versus fluorescent test antibody: 97.4% of agreement; ELISA versus fluorescent test antibody: 96.1% of agreement). In addition, the use of the Receiver Operating Characteristic (ROC) curve, showing the changes of sensitivity and specificity as a function of the possible values of each threshold, indicated that sera with titers between 15-20 IU/ml should be interpreted very cautiously.

[Subconjunctival localization of a Wuchereria bancrofti adult female]. / Localisation sous-conjonctivale d'une femelle adulte de Wuchereria bancrofti.

The authors describe a case of conjunctival localization of a living adult Wuchereria bancrofti female observed in a 6 year old native Haitian girl, two years after her arrival in France. The adult was surgically removed from the conjunctiva. Microfilariae were evidenced in blood samples obtained at midnight. This is the first case of sub-conjunctival localization of W. bancrofti. This case stresses the necessity to identify the filaria by studying the microfilariae in blood samples obtained at different times of the nycthemere and/or by observing the adult after surgical extraction. The presence of a Loa, a Dirofilaria, a Mansonella, or a Wuchereria calls for different medical therapies.

[Orbital zygomycosis (mucormycosis) in a healthy child. Treatment with ketoconazole]. / Zygomycose (mucormycose) orbitale chez un enfant sain. Traitement par le kétoconazole.

A case of orbital zygomycosis, probably mucormycosis, histologically demonstrated was observed in a healthy host. The etiologic agent could not be identified because of the unsuccessful cultures. No clinical antecedent allowed us to suppose that an immunological deficiency statement was present. It seemed that the fungus did not penetrates by the classical nasal and sinusal pathways. The fungus inoculation probably resulted from a subocular traumatism. The ketoconazole treatment, the only one possible in our case, was efficient.