Exploring ionic liquids based on pyrrolidinium and imidazolium cations with low toxicity towards Escherichia coli for designing sustainable bioprocesses.

Ionic liquids (ILs) are widely applied in many bioprocesses involving microorganisms due to their unique properties. In this work, the toxicity of imidazolium and pyrrolidinium ionic liquids towards E. coli., a bacterium for which there are limited toxicity data in the literature, was determined. For its simplicity, the nephelometry method was used to estimate ionic liquid toxicity values. The influence of the cation and the alkyl chain length of the cation and anion was analysed. Pyrrolidinium cations were seen to be less toxic than imidazolium cations, while an increase in the alkyl chain length of both pyrrolidinium and imidazolium cations increased the toxicity. Among the anions studied, dimethylphosphate ([Me2PO4]) was the less toxic, while the EC50 for the ionic liquid 1-butyl-3-methylpyrrolidinium dimethylphosphate ([C1C4Pyr][Me2PO4]) was close to 200 mM. Furthermore, a dicationic ionic liquid based on imidazolium and pyrrolidinium cations was synthetized and its toxicity toward E. coli was analysed, maintaining a growth rate of 100 % in the range 0-0.76 mM. The methodology used in this work allows to easily find the less toxic ionic liquids that are biocompatible with E. coli to be used in new bioprocesses.

In-situ soil greenhouse gas fluxes under different cryptogamic covers in maritime Antarctica.

Soils can influence climate by sequestering or emitting greenhouse gases (GHG) such as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). We are far from understanding the direct influence of cryptogamic covers on soil GHG fluxes, particularly in areas free of potential anthropogenic confounding factors. We assessed the role of well-developed cryptogamic covers in soil attributes, as well as in the in-situ exchange of GHG between Antarctic soils and the atmosphere during the austral summer. We found lower values of soil organic matter, total organic carbon, and total nitrogen in bare areas than in soils covered by mosses and, particularly, lichens. These differences, together with concomitant decreases and increases in soil temperature and moisture, respectively, resulted in increases in in-situ CO2 emission (i.e. ecosystem respiration) and decreases in CH4 uptake but no significant changes in N2O fluxes. We found consistent linear positive and negative relationships between soil attributes (i.e. soil organic matter, total organic carbon and total nitrogen) and CO2 emissions and CH4 uptake, respectively, and polynomial relationships between these soil attributes and net N2O fluxes. Our results indicate that any increase in the area occupied by cryptogams in terrestrial Antarctic ecosystems (due to increased growing season and increasingly warming conditions) will likely result in parallel increases in soil fertility as well as in an enhanced capacity to emit CO2 and a decreased capacity to uptake CH4. Such changes, unless offset by parallel C uptake processes, would represent a paradigmatic example of a positive climate change feedback. Further, we show that the fate of these terrestrial ecosystems under future climate scenarios, as well as their capacity to exchange GHG with the atmosphere might depend on the relative ability of different aboveground cryptogams to thrive under the new conditions.

Synthesis of low cost organometallic-type catalysts for their application in microbial fuel cell technology.

Microbial fuel cells (MFCs) are a promising technology that generates electricity from several biodegradable substrates and wastes. The main drawback of these devices is the need of using a catalyst for the oxygen reduction reaction at the cathode, which makes the process relatively expensive. In this work, two low cost materials are tested as catalysts in MFCs. A novel iron complex based on the ligand n-phenyledenparaethoxy aniline has been synthesized and its performance as catalyst in single chamber MFCs containing ionic liquids has been compared with a commercial inorganic material such as Raney nickel. The results show that both materials are suitable for bioenergy production and wastewater treatment in the systems. Raney nickel cathodes allow MFCs to reach a maximum power output of 160 mW.m-3 anode, while the iron complex offers lower values. Regarding the wastewater treatment capacity, MFCs working with Raney nickel-based cathodes reach higher values of chemical oxygen demand removal (76%) compared with the performance displayed by the cathodes based on Fe-complex (56%).

Assessment of the effects of discontinuous sources of contamination through biomarker analyses on caged mussels.

The present study analysed potential adverse effects of discontinuous sources of contamination, namely the discharge of a combined sewer overflow (CSO) and of runoff in an urban area, the Bay of Santander (North Iberian Peninsula). Water samples and caged mussels were used to analyse concentrations of contaminants and biological responses. Mussels (Mytilus galloprovincialis) were transplanted to a marina receiving runoff from a petrol station and to a CSO discharge site. Samples were collected in synchrony with heavy rains along 62days. Lysosomal membrane stability (LMS) and acyl-CoA oxidase (AOX) activity were measured as core biomarkers and were analysed at all sampling times. Histopathology of digestive gland and gonads, transcription levels of vitellogenin gene, volume density of black silver deposits and micronuclei formation were measured at initial and final stages of the transplant. Chemical analyses of metals, polycyclic aromatic hydrocarbons (PAHs) and endocrine disruptors were performed in water samples and mussel flesh. Mussels accumulated low concentrations of contaminants, which is in accordance with results obtained from exposure biomarkers. AOX activity decreased in all transplanted mussels after the first heavy rain, but this change seems to be related to the seasonal pattern of the enzyme activity. Mussels located close to the CSO discharge site showed a reduction in LMS after the first rain event, when compared to mussels before the transplant and to mussels from the reference location. However, this was attributable to natural environmental changes rather than to pollution. Values of the rest of analysed biomarkers were below threshold values reported for the study area.

Phytoextraction of heavy metals from a multiply contaminated dredged sediment by chicory (Cichorium intybus L.) and castor bean (Ricinus communis L.) enhanced with EDTA, NTA, and citric acid application.

The remediation of contaminated dredged sediments is necessary to eliminate the risk towards human beings or the environment when there is disposal on land. A greenhouse experiment was carried out to evaluate the chemically assisted phytoextraction to clean up dredged sediment contaminated with Cr, Cu, Pb, and Zn. The ability of castor bean and chicory to absorb, translocate, and accumulate metals from sediment to root and shoot was evaluated by applying EDTA (5 mM), NTA (5 mM), and citric acid (60 mM) to sediment, before the harvest. Citric acid 60 mM was the most effective treatment in increasing Cr, Cu, and Pb in castor bean and chicory shoot. Chicory could accumulate 1730 mg Cr kg-1 in shoot, and had greater values than one for the bioaccumulation and translocation factors when citric acid was added to the sediment. But, the Cr percentages removed per harvest of chicory were 0.05% and were lower for Cu, Pb, and Zn due to low biomass obtained. Citric acid-assisted phytoextraction with chicory can be a promising short time solution to reduce Cr concentration in sediment and reach the Cr level guide for industrial land use only if suitable agronomic practices could be implemented to increase crop yield.

Experiencia con insulina degludec en pacientes diabéticos Tipo 1 del Hospital San Juan de Dios Santiago / Experience with degludec insulin in Type 1 diabetic patients at the San Juan de Dios Hospital

OBJECTIVE: To study the efficacy and safety of degludec insulin in Type 1 diabetic patients. PATIENTS AND METHOD: In a prospective study, 230 type 1 diabetics patients, average aged 34 years age and 14 years of diagnosis of diabetes and treated with two doses of insulin glargine U-100, were changed to degludec. Patients had glycosylated hemoglobins (HbA1c) greater than 10 percent. Results were recorded at 3 and 6 months with parameters clinical, biochemical, insulin requirements per kilogram of weight (U/kg/wt) and hypoglycemia. Capillary glycemia was evaluated three times a day and the dose of insulin degludec every two weeks. The statistical analysis used was average and rank, standard deviation, normal Swilk test, categorical Chi2 and continuous ANOVA or Kwallis, and p < 0.05. A psychological survey was conducted to evaluate satisfaction with the new treatment. RESULTS: Fasting blood glucose decreased from 253 (range 243-270) at 180 mg/dl (172-240) at 3 months and at 156 (137-180) at 6 months after the change insulin (p < 0.05). HbA1c, initially 10.6 percent (10.4-12.2) decreased to 8.7 percent (9.3-10.1) and 8.3 percent (8.7-9.7) at 3 and 6 months, respectively (p < 0.05). There was a decrease in basal insulin requirements from 0.7 to 0.4 U/kg/60 percent reduction in hypoglycaemia; both mild and moderate and severe. Isolated nocturnal hypoglycaemias were recorded in only 4 patients in this group. CONCLUSION: Six months of treatment with degludec insulin reduces fasting blood glucose, glycosylated hemoglobin and hypoglycemia, both mild and moderate severe and nocturnal, which makes this new ultra-long acting basal insulin a safe and effective tool for the management of type 1 diabetics patients

Ionic liquid technology to recover volatile organic compounds (VOCs).

Volatile organic compounds (VOCs) comprise a wide variety of carbon-based materials which are volatile at relatively low temperatures. Most of VOCs pose a hazard to both human health and the environment. For this reason, in the last years, big efforts have been made to develop efficient techniques for the recovery of VOCs produced from industry. The use of ionic liquids (ILs) is among the most promising separation technologies in this field. This article offers a critical overview on the use of ionic liquids for the separation of VOCs both in bulk and in immobilized form. It covers the most relevant works within this field and provides a global outlook on the limitations and future prospects of this technology. The extraction processes of VOCs by using different IL-based assemblies are described in detail and compared with conventional methods This review also underlines the advantages and limitations posed by ionic liquids according to the nature of the cation and the anions present in their structure and the stability of the membrane configurations in which ILs are used as liquid phase.

Relationships between lines of evidence of pollution in estuarine areas: Linking contaminant levels with biomarker responses in mussels and with structure of macroinvertebrate benthic communities.

Data obtained in a pollution survey performed in estuarine areas were integrated using multivariate statistics. The sites selected for the study were areas affected by treated and untreated urban discharges, harbours or industrial activities as well as reference sites. Mussels were transplanted to each site and after different times of exposure, samples of water, sediments and mussels were collected. Biomarkers were analysed on mussels after 3 and 21 days of transplant whereas concentrations of contaminants were measured in water, sediments and mussels after 21 days of transplant. The structure of macroinvertebrate benthic communities was studied in sediment samples. Studied variables were organised into 5 datasets, each one constituting a line of evidence (LOE): contaminants in water, contaminants in sediments, contaminants accumulated by transplanted mussels, biomarkers in transplanted mussels and changes in the structure of macroinvertebrate benthic communities of each sampling site. Principal Component Analysis (PCA) identified the variables of each LOE best explaining variability among sites. In order to know how LOEs relate to each other, Pearson's correlations were performed. Contaminants in sediments were not correlated with the rest of LOEs. Contaminants in water were significantly correlated with contaminants and biomarkers in mussels and with structure of macroinvertebrate benthic communities. Similarly, significant correlations were found between contaminants and biomarkers in mussels and between biomarkers in mussels and structure of macroinvertebrate benthic communities. In conclusion, biomarker responses give relevant information on pollution in estuarine areas and provide a link between chemical and ecological statuses of water bodies in the context of the Water Framework Directive.

Microalgae as substrate in low cost terracotta-based microbial fuel cells: Novel application of the catholyte produced.

In this work, the by-product generated during the operation of cylindrical MFCs, made out of terracotta material, is investigated as a feasible means of degrading live microalgae for the first time. In addition to the low cost materials of this design, the reuse of the solution produced in the cathode renders the technology truly green and capable of generating bioenergy. In this study, the effect of a light/dark cycle or dark conditions only on the digestion of live microalgae with the catholyte is investigated. The results show that a combination of light/dark improves degradation and allows algae to be used as substrate in the anode. The addition of 12.5mL of a 1:1 mix of catholyte and microalgae (pre-digested over 5days under light/dark) to the anode, increases the power generation from 7µW to 44µW once all the organic matter in the anode had been depleted.

Measuring biological responses at different levels of organisation to assess the effects of diffuse contamination derived from harbour and industrial activities in estuarine areas.

To evaluate the effects of diffuse contamination, biological measurements were applied in a scrap cargo harbour, a marina and an industrial area. Metal accumulation and biomarkers (survival in air, digestive gland and gonad histopathology, lysosomal membrane stability, intralysosomal metal accumulation, transcription of vitellogenin and MT20, peroxisome proliferation and micronuclei formation) were measured in transplanted mussels, together with metrics of benthic invertebrates. Benthic species were classified into ecological groups and univariate indexes were calculated. The marina showed high richness (16) and percentage of opportunistic species (55.1%) and low metal accumulation. Mussels in the scrap cargo harbour showed high metal accumulation, up-regulation of MT20 transcription, reduced health status (LP<6 min) and increased micronuclei frequencies (up to 11.3‰). At the industrial area, low species richness (4) and badly organised assemblages were detected and chemical analyses indicated significant amounts of bioavailable metals. Overall, selected biological measurements showed potential for the assessment of diffuse contamination.

Disfunción sexual en la mujer diabética pre y postmenopáusica / Sexual dysfunction in women with diabetes in pre and postmenopausic state

Objective: female sexual dysfunction (FSD) in diabetic women, is a topic poorly studied. The aim of this study is to determine the prevalence of FSD in typ1 1 and typ2 diabetic patients (T1D and T2D) compared with non diabetic controls. Patients and Method: interview under written consent 24 diabetic patients attended at Diabetes Unit of the San Juan de Dios Hospital and 24 healthy controls. Inclusion criteria: diagnosis of diabetes mellitus over one year, age 18-75 years old and stable partner for over a year. Exclusion criteria: antidepressants treatment. The validated survey by Rosen et al. was applied. Female Sexual Function Index (FSFI), of 19 questions that assess 6 areas of sexual function: desire, lubrication, excitement, orgasm, satisfaction and pain. A total score of 26.55 or less diagnosed DSF. In diabetic patients the metabolic control, lipid profile, creatinine and glycated hemoglobin A1c (HbA1c) was recorded. Statistical analysis was performed using median, range and Mann Whitney test. Percentages of sexual dysfunction was analysed by chi². It was considered significant at p < 0.05. Results: the results of the FSFI survey were divided and related to menopause. In premenopausal diabetic group (n = 11), the average score was 31.1 versus 32.5 in controls (NS) and in postmenopausal diabetic group (n = 13) the average score was 23,1 versus 28,5 (p = 0.05). The overall frequency of DSF in premenopausal diabetic women was 27.3 percent and 6.3 percent in controls (NS), in postmenopausal reached 69.2 percent and25.0 percent in controls (p = 0.01 ). Conclusion: in diabetic patients sexual dysfunction was more frequent than in controls; in premenopausal women the most affected area is the excitement and in postmenopausal women was lubrication.

[Ketosis prone type 2 diabetes (KPD)]. / Diabetes Mellitus tipo 2 con tendencia a la cetosis: Caso clínico.

Ketosis prone type 2 diabetes (KPD) is presently a well-defined clinical entity, characterized by a debut with severe hyperglycemia and ketoacidosis similar to the presenting form of Type 1 diabetes mellitus (DM1). However, it appears in subjects with Type 2 diabetes mellitus (DM2) phenotype. This situation is caused by an acute, reversible dysfunction of the beta cell in individuals with insulin resistance. Once the acute stage subsides, patients behave as having a DM2 and do not require insulin treatment. They should be kept on a diet and oral hypoglycemic drugs due to their susceptibility to have recurrent acute ketotic decompensations.

Diabetes Mellitus tipo 2 con tendencia a la cetosis: Caso clínico / Ketosis prone type 2 diabetes (KPD)

Ketosis prone type 2 diabetes (KPD) is presently a well-defined clinical entity, characterized by a debut with severe hyperglycemia and ketoacidosis similar to the presenting form of Type 1 diabetes mellitus (DM1). However, it appears in subjects with Type 2 diabetes mellitus (DM2) phenotype. This situation is caused by an acute, reversible dysfunction of the beta cell in individuals with insulin resistance. Once the acute stage subsides, patients behave as having a DM2 and do not require insulin treatment. They should be kept on a diet and oral hypoglycemic drugs due to their susceptibility to have recurrent acute ketotic decompensations.

Metformina asociada a insulinoterapia en pacientes diabéticos tipo 1 / Metformin associated with insulin therapy in type 1 diabetic patients

In patients with diabetes type 1 (T1D) glycemic control remains suboptimal, despite the availability of new insulin analogues and continuous infusion systems. Metformin may be a complementary therapy regarding to intensified insulin therapy since a significant percentage of T1D have insulin resistance (IR). Objective: To analyze the clinical, anthropometric and metabolic effects of the combination of metformin to insulin therapy in T1D patients. Subjects and Method: 34 T1D patients, 15 men and 19 women, mean age 41 years (range 20-64) metformin 850 mg / day was associated for 6 months (group 1) and retrospectively evaluated 18 T1D, 9 men and 9 women, age average 34 years (range 17-58), who received metformin for 36 months (group 2). It was recorded before and after treatment with metformin: nutritional status, waist circumference, index waist / hip, glucose fasting, glycosylated hemoglobin (HbA1c), HDL cholesterol, triglycerides, systolic and diastolic blood pressure (BP), glucose uptake (UG) and insulin dose (U/kg). Statistical analyses. Clinical and biochemical parameters were expressed as median, range or percentage (percent). For the statistical significance were used chi2and Fisher exact and Mann Whitney test; and was established as significant at p <0.05. Results: In group 1 significantly decreased waist circumference in men and women and improved fasting glucose, HbA1c, systolic blood pressure and triglycerides. In group 2, waist circumference and systolic blood pressure was also reduced. Conclusion: In T1D patients with clinical signs of IR the association of metformin to insulin therapy may be useful.

Discovering less toxic ionic liquids by using the Microtox® toxicity test.

New Microtox® toxicity data of 16 ionic liquids of different cationic and anionic composition were determined. The ionic liquids 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, [BMPyr(+)][TFO(-)], 1-butyl-1-methylpyrrolidinium chloride, [BMPyr(+)][Cl(-)], hydroxypropylmethylimidazolium fluoroacetate, [HOPMIM(+)][FCH2COO(-)], and hydroxypropylmethylimidazolium glycolate [HOPMIM(+)][glycolate(-)] were found to be less toxic than conventional organic solvent such as chloroform or toluene, accoding the Microtox® toxicity assays. The toxicity of pyrrolidinium cation was lower than the imidazolium and pyridinium ones. It was found that the inclusion of an hydroxyl group in the alkyl chain length of the cation also reduce the toxicity of the ionic liquid. To sum up, the Microtox® toxicity assays can be used as screening tool to easily determined the toxicity of a wide range of ionic liquids and the toxicity data obtained could allow the obtention of structure-toxicity relationships to design less toxic ionic liquids.

Alteraciones hematológicas en la diabetes mellitus / Blood disorders in diabetes mellitus

Although it has been treated in a limited way the relationship between diabetes and hematopoietic system, there is evidence demonstrating thedeleterious effect of hyperglycemia on the three cell lines: red blood cells, white cells and platelets. Different forms of anemia associated with hyperglycemia are analyzed and erythrocyte alterations observed in diabetes. In chronic decompensated patients have been demonstrated alterationsof monocytes, lymphocytes and polymorphonuclear particularly, with decreased chemotaxis, adherence, phagocytosis and opsonization. Hyperglycemia determines a prothrombotic state by platelet hyperreactivity, which is a marker of inflammation...

Diabéticos tipo 1 portadores de síndrome metabólico: cuantificación de la resistencia a la insulina / Type 1 diabetics patients carriers of metabolic syndrome: quantification of insulin resistance

The presence of insulin resistance (IR) has been indirectly assessed in Type 1 Diabetics (T1DM) through the detection of Metabolic Syndrome (MS), by applying criteria for Type 2 Diabetics(T2DM). In the EDC study (the Pittsburg Epidemiology of Diabetes Complications) a formula applicable to T1DM was validated, quantifying IR through the glucose uptake (GU) employing the usual clinical and laboratory parameters, in patients with HbA1c < 11.4 percent. Objectives: To determine in T1DM whether there exists a relationship between the presence of MS according to the Modified NCEP/ATPIII criteria and IR quantification through assessment of the glucose uptake or GU. Patients and Method: The modified NCEP/ATPIII criteria were applied to 150 T1DM patients, and those with more than 3 altered parameters were classified as MS carriers. IR was quantified through the glucose uptake (GU), applying the formula for Estimated Glucose Disposal Rate (GDR-EDC). Results: 26.6 percent of the T1DM (40 patients) complied with the modified NCEP/ATPIII criteria. When the formula for GU was applied (31 patient), 90.3 percent of the T1DM showed insulin resistance (GU value < 8.77). And when applied to 124 patients (T1DM with and without MS and HbA1c < 11,4 percent) 75 percent showed IR...

Assessing the effects of treated and untreated urban discharges to estuarine and coastal waters applying selected biomarkers on caged mussels.

To assess effects of urban discharges, biomarkers were measured in caged mussels in northern Iberian Peninsula. Lysosomal membrane stability and histopathology of gonad and digestive gland were analysed as general effect biomarkers. Exposure to specific pollutants was evaluated by autometallographical detection of metals, peroxisomal acyl-CoA oxidase activity, micronucleus test and transcription levels of vitellogenin and MT20 genes. Health status of mussels was impaired after 3 days of caging at the untreated outfall discharge and at the waste water treatment plant effluent discharge to the estuary. The most relevant finding was the significant up-regulation of vitellogenin gene transcription in male mussels exposed to the untreated outfall discharge. Metals and xenoestrogenic endocrine disruptors were bioavailable in some discharges and disturbed the health status of mussels. Biomarkers were effective in the assessment of effects of urban discharges and could be implemented in operative controls required to assess the risks associated to effluent discharges.

Effect of copper and lead on two consortia of phototrophic microorganisms and their capacity to sequester metals.

The roles of consortia of phototrophic microorganisms have been investigated in this paper to determine their potential role to tolerate or resist metals and to capture them from polluted cultures. With this purpose, two consortia of microorganisms: on one hand, Geitlerinema sp. DE2011 (Ge) and Scenedesmus sp. DE2009 (Sc) (both identified in this paper by molecular biology methods) isolated from Ebro Delta microbial mats, and on the other, Spirulina sp. PCC 6313 (Sp) and Chroococcus sp. PCC 9106 (Ch), from Pasteur culture collection were polluted with copper and lead. In order to analyze the ability of these consortia to tolerate and capture metals, copper and lead were selected, because both have been detected in Ebro Delta microbial mats. The tolerance-resistance to copper and lead for both consortia was determined in vivo and at cellular level by Confocal Laser Scanning Microscopy (CLSM-λscan function). The results obtained demonstrate that both consortia are highly tolerant-resistant to lead and that the limits between the copper concentration having cytotoxic effect and that having an essential effect are very close in these microorganisms. The capacity of both consortia to capture extra- and intracellular copper and lead was determined by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) respectively, coupled to an Energy Dispersive X-ray detector (EDX). The results showed that all the microorganisms assayed were able to capture copper extracellularly in the extrapolymeric substances, and lead extra- and intracellularly in polyphosphate inclusions. Moreover, the studied micro-organisms did not exert any inhibitory effect on each other's metal binding capacity. From the results obtained in this paper, it can be concluded that consortia of phototrophic microorganisms could play a very important role in biorepairing sediments polluted by metals, as a result of their ability to tolerate or resist high concentrations of metals and to bioaccumulate them, extra- and intracellulary.