Synthesis of a novel magnetic nanomaterial for the development of a multielemental speciation method of lead, mercury, and vanadium via HPLC-ICP MS.

A new magnetic functionalized material based on graphene oxide magnetic nanoparticles named by us, M@GO-TS, was designed and characterized in order to develop a magnetic solid-phase extraction method (MSPE) to enrich inorganic and organic species of lead, mercury, and vanadium. A flow injection (FI) system was used to preconcentrate the metallic and organometallic species simultaneously, while the ultra-trace separation and determination of the selected species were achieved by high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP MS). Therefore, preconcentration and separation/determination processes were automated and conducted separately. To the best of our knowledge, this is the first method combining an online MSPE and HPLC-ICP MS for multielemental speciation. Under the optimized conditions, the enrichment factor obtained for PbII, trimethyllead (TML), HgII, methylmercury (MetHg), and VV was 27. The calculated LOD for all studied species were as follows: 5 ng L-1, 20 ng L-1, 2 ng L-1, 10 ng L-1, and 0.4 ng L-1, respectively. The RSD values calculated with a solution containing 0.5 µg L-1 of all species were between 2.5 and 4.5%. The developed method was validated by analyzing Certified Reference Materials TMDA 64.3 for total concentration and also by recovery analysis of the species in human urine from volunteers and a seawater sample collected in Málaga. The t statistical test showed no significant differences between the certified and found values for TMDA 64.3. All the recoveries obtained from spiked human urine and seawater samples were close to 100%. All samples were analyzed using external calibration. The developed method is sensitive and promising for routine monitoring of the selected species in environmental waters and biological samples.

A Molecularly Imprinted Polypyrrole/GO@Fe3O4 Nanocomposite Modified Impedimetric Sensor for the Routine Monitoring of Lysozyme.

Lysozyme (LYS) applications encompass anti-bacterial activity, analgesic, and anti-inflammatory effects. In this work, a porous framework that was based on the polymerization of pyrrole (PPy) in the presence of multi-functional graphene oxide/iron oxide composite (GO@Fe3O4) has been developed. Oxygen-containing and amine groups that were present in the nanocomposite were availed to assembly LYS as the molecularly imprinted polymer (MIP) template. The synthesized material (MIPPy/GO@Fe3O4) was electrodeposited on top of a gold microelectrode array. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) were used to confirm the adequate preparation of GO@Fe3O4, and the characterization of the resulting molecularly imprinted electrochemical sensor (MIECS) was carried out by electrochemical impedance spectrometry (EIS), FT-IR analysis, and scanning electron microscopy (SEM). The impedimetric responses were analyzed mathematically by fitting to a Q(Q(RW)) equivalent circuit and quantitative determination of LYS was obtained in a linear range from 1 pg/mL to 0.1 µg/mL, presenting good precision (RSD ≈ 10%, n = 5) and low limit of detection (LOD = 0.009 pg/mL). The fabrication of this device is relatively simple, scalable, rapid, and economical, and the sensor can be used up to nine times without disintegration. The MIECS was successfully applied to the determination of LYS in fresh chicken egg white sample and in a commercial drug, resulting in a straightforward platform for the routine monitoring of LYS.

Reproductive phenology and morphology of Macrocystis pyrifera (Laminariales, Ochrophyta) from southern New Zealand in relation to wave exposure1.

Macrocystis pyrifera is a major habitat forming kelp in coastal ecosystems of temperate regions of the northern and southern hemispheres. We investigated the seasonal occurrence of adult sporophytes, morphological characteristics, and reproductive phenology at two sites within a wave-protected harbour and two wave-exposed sites in southern New Zealand every 3-4 months between 2012 and 2013. Seasonality in reproduction was assessed via the number of sporophylls, the occurrence of sori on sporophylls, and non-sporophyllous laminae (fertile pneumatocyst-bearing blades and fertile apical scimitars), meiospore release, and germination. We found that M. pyrifera was present and reproductive year-round in three of the four sites, and patterns were similar for the wave-exposure conditions. Sori were found on pneumatocyst-bearing blades and apical scimitars in addition to the sporophylls, and viable meiospores were released from all three types of laminae. Morphological variations between sites with different wave exposure indicate that sporophytes from wave-protected sites have bigger blades and holdfasts and are longer than those from wave-exposed sites. We discuss the implications of these biological variables for the ecology of M. pyrifera inhabiting different wave exposure environments in southern New Zealand.

Nitrogen sufficiency enhances thermal tolerance in habitat-forming kelp: implications for acclimation under thermal stress.

Local and global changes associated with anthropogenic activities are impacting marine and terrestrial ecosystems. Macroalgae, especially habitat-forming species like kelp, play critical roles in temperate coastal ecosystems. However, their abundance and distribution patterns have been negatively affected by warming in many regions around the globe. Along with global change, coastal ecosystems are also impacted by local drivers such as eutrophication. The interaction between global and local drivers might modulate kelp responses to environmental change. This study examines the regulatory effect of NO3- on the thermal plasticity of the giant kelp Macrocystis pyrifera. To do this, thermal performance curves (TPCs) of key temperature-dependant traits-growth, photosynthesis, NO3- assimilation and chlorophyll a fluorescence-were examined under nitrate replete and deplete conditions in a short-term incubation. We found that thermal plasticity was modulated by NO3- but different thermal responses were observed among traits. Our study reveals that nitrogen, a local driver, modulates kelp responses to high seawater temperatures, ameliorating the negative impacts on physiological performance (i.e. growth and photosynthesis). However, this effect might be species-specific and vary among biogeographic regions - thus, further work is needed to determine the generality of our findings to other key temperate macroalgae that are experiencing temperatures close to their thermal tolerance due to climate change.

Comparative Study of Synthesis Methods to Prepare New Functionalized Adsorbent Materials Based on MNPs-GO Coupling.

In this work, the synthesis of new adsorbent nanomaterials based on the coupling of magnetic nanoparticles and graphene oxide (MNPs-GO) was addressed. Separately, MNPs and GO have adsorbent properties of great interest, but their use involves certain difficulties. The coupling seeks compensation for their disadvantages, while maintaining their excellent properties. Three different routes to synthesize coupled MNPs-GO were studied and are compared in this work. The three synthesized materials were functionalized with chelating groups: [1,5-bis (di-2-pyridyl) methylene] thiocarbonohydrazide (DPTH) and [1,5-bis(2-pyridyl)3-sulfophenylmethylene] thiocarbonohydrazide (PSTH). The new adsorbent nanomaterials were characterized adequately. Moreover, their capacities of adsorption toward heavy and noble metals were determined, in order to apply them as extractants in magnetic solid-phase extraction to preconcentrate metals in environmental samples. The results showed that one of the routes provided nanomaterials with better adsorbent characteristics and higher yields of functionalization.

Responses of macroalgae to CO2 enrichment cannot be inferred solely from their inorganic carbon uptake strategy.

Increased plant biomass is observed in terrestrial systems due to rising levels of atmospheric CO2, but responses of marine macroalgae to CO2 enrichment are unclear. The 200% increase in CO2 by 2100 is predicted to enhance the productivity of fleshy macroalgae that acquire inorganic carbon solely as CO2 (non-carbon dioxide-concentrating mechanism [CCM] species-i.e., species without a carbon dioxide-concentrating mechanism), whereas those that additionally uptake bicarbonate (CCM species) are predicted to respond neutrally or positively depending on their affinity for bicarbonate. Previous studies, however, show that fleshy macroalgae exhibit a broad variety of responses to CO2 enrichment and the underlying mechanisms are largely unknown. This physiological study compared the responses of a CCM species (Lomentaria australis) with a non-CCM species (Craspedocarpus ramentaceus) to CO2 enrichment with regards to growth, net photosynthesis, and biochemistry. Contrary to expectations, there was no enrichment effect for the non-CCM species, whereas the CCM species had a twofold greater growth rate, likely driven by a downregulation of the energetically costly CCM(s). This saved energy was invested into new growth rather than storage lipids and fatty acids. In addition, we conducted a comprehensive literature synthesis to examine the extent to which the growth and photosynthetic responses of fleshy macroalgae to elevated CO2 are related to their carbon acquisition strategies. Findings highlight that the responses of macroalgae to CO2 enrichment cannot be inferred solely from their carbon uptake strategy, and targeted physiological experiments on a wider range of species are needed to better predict responses of macroalgae to future oceanic change.

Copper pollution exacerbates the effects of ocean acidification and warming on kelp microscopic early life stages.

Ocean warming (OW), ocean acidification (OA) and their interaction with local drivers, e.g., copper pollution, may negatively affect macroalgae and their microscopic life stages. We evaluated meiospore development of the kelps Macrocystis pyrifera and Undaria pinnatifida exposed to a factorial combination of current and 2100-predicted temperature (12 and 16 °C, respectively), pH (8.16 and 7.65, respectively), and two copper levels (no-added-copper and species-specific germination Cu-EC50). Meiospore germination for both species declined by 5-18% under OA and ambient temperature/OA conditions, irrespective of copper exposure. Germling growth rate declined by >40%·day-1, and gametophyte development was inhibited under Cu-EC50 exposure, compared to the no-added-copper treatment, irrespective of pH and temperature. Following the removal of copper and 9-day recovery under respective pH and temperature treatments, germling growth rates increased by 8-18%·day-1. The exception was U. pinnatifida under OW/OA, where growth rate remained at 10%·day-1 before and after copper exposure. Copper-binding ligand concentrations were higher in copper-exposed cultures of both species, suggesting that ligands may act as a defence mechanism of kelp early life stages against copper toxicity. Our study demonstrated that copper pollution is more important than global climate drivers in controlling meiospore development in kelps as it disrupts the completion of their life cycle.

Photosynthesis and nitrogen uptake of the giant kelp Macrocystis pyrifera (Ochrophyta) grown close to salmon farms.

Finfish aquaculture is an activity that has experienced an explosive global development, but presents several environmental risks, such as high nitrogen outputs with potential eutrophication consequences. Therefore, the integration of seaweed aquaculture with the aim of decreasing nitrogen emissions associated with intensive salmon farming has been proposed as a bioremediation solution. Ecophysiological knowledge about seaweeds cultured close to farming cages is, however, still rudimentary. We experimentally studied the growth and physiological responses of Macrocystis pyrifera (Linnaeus) C. Agardh in a suspended culture system near a commercial salmon farm at three culture depths in order to understand its productivity performance. The results showed maximum growth responses at intermediate depths (3 m) as opposed to near the surface (1 m) or at a deeper culture level (6 m). At 6 m depth, light limitations were detected, whereas the sporophytes growing at 1 m depth responded to high irradiances, especially in late spring and summer, where they were more intensely exposed to decay of photosynthesis than individuals from other depths. Accordingly, photosynthetic pigment concentrations (chlorophyll a and c, and fucoxonthin) were higher during low-light seasons (winter and early spring) but decreased during the summer. On the other hand, although both nitrogen uptake and Nitrate Reductase (NR) activity varied seasonally, increasing significantly in spring and summer, these variables were not affected by culture depth. Therefore, the optimal culture depth of M. pyrifera near salmon farms appears to be a physiological integration between nitrogen supply and demand, which is modulated by plant acclimation to the seasonal change in light and temperature. The results allow to discuss about the environmental constrains of M. pyrifera in an ecophysiological context to improve the understanding of its aquaculture, and to contribute relevant information on the use of this species in bioremediation.

Growth, ammonium metabolism, and photosynthetic properties of Ulva australis (Chlorophyta) under decreasing pH and ammonium enrichment.

The responses of macroalgae to ocean acidification could be altered by availability of macronutrients, such as ammonium (NH4+). This study determined how the opportunistic macroalga, Ulva australis responded to simultaneous changes in decreasing pH and NH4+ enrichment. This was investigated in a week-long growth experiment across a range of predicted future pHs with ambient and enriched NH4+ treatments followed by measurements of relative growth rates (RGR), NH4+ uptake rates and pools, total chlorophyll, and tissue carbon and nitrogen content. Rapid light curves (RLCs) were used to measure the maximum relative electron transport rate (rETRmax) and maximum quantum yield of photosystem II (PSII) photochemistry (Fv/Fm). Photosynthetic capacity was derived from the RLCs and included the efficiency of light harvesting (α), slope of photoinhibition (ß), and the light saturation point (Ek). The results showed that NH4+ enrichment did not modify the effects of pH on RGRs, NH4+ uptake rates and pools, total chlorophyll, rETRmax, α, ß, Fv/Fm, tissue C and N, and the C:N ratio. However, Ek was differentially affected by pH under different NH4+ treatments. Ek increased with decreasing pH in the ambient NH4+ treatment, but not in the enriched NH4+ treatment. NH4+ enrichment increased RGRs, NH4+ pools, total chlorophyll, rETRmax, α, ß, Fv/Fm, and tissue N, and decreased NH4+ uptake rates and the C:N ratio. Decreased pH increased total chlorophyll content, rETRmax, Fv/Fm, and tissue N content, and decreased the C:N ratio. Therefore, the results indicate that U. australis growth is increased with NH4+ enrichment and not with decreasing pH. While decreasing pH influenced the carbon and nitrogen metabolisms of U. australis, it did not result in changes in growth.

Percutaneous CT-Guided Sympathicolysis with Radiofrequency for the Treatment of Palmar Hyperhidrosis.

PURPOSE: To evaluate the benefits of computed tomography (CT)-guided percutaneous sympathicolysis with radiofrequency in patients with primary palmar hyperhidrosis (PPHH) in terms of safety, patient satisfaction, and short- and long-term efficacy. MATERIALS AND METHODS: A total of 139 procedures in 108 patients (mean age, 29.89 y ± 10.94), including 50 men and 58 women, with PPHH and therapy-resistance of nonsurgical treatments were retrospectively analyzed. Treatment was performed bilaterally at T2, T3, and T4 levels, reaching 90°C during 8 minutes. Technical success, immediate efficacy, and presence of complications were analyzed. For follow-up, the Hyperhidrosis Disease Severity Scale was used to evaluate the hyperhidrosis before, at one month, and in the long-term through a survey of 42 patients. Patients' satisfaction and complications were also recorded. RESULTS: The technical success rate was 98.56%. The increase in palmar skin temperature was 4.88°C ± 1.85. A total of 85.3% of participants had completely dry hands immediately after treatment. The mean follow-up time was 41.34 months (range, 6-62 mo). One month after treatment, the response rate was 77.38% (P < .001). At long-term follow-up, the response rate was 69.04% (P < .001). Two major complications were observed (1.8%), 52.38% of patients were satisfied, and 59.52% of patients presented compensatory hyperhidrosis at long-term follow-up. CONCLUSIONS: Percutaneous CT-guided sympathicolysis is a safe and effective technique for the treatment of PPHH and can be considered as a second choice in patients in whom other nonsurgical therapeutic options have failed, despite the compensatory hyperhidrosis rates.

Ocean acidification and kelp development: Reduced pH has no negative effects on meiospore germination and gametophyte development of Macrocystis pyrifera and Undaria pinnatifida.

The absorption of anthropogenic CO2 by the oceans is causing a reduction in the pH of the surface waters termed ocean acidification (OA). This could have substantial effects on marine coastal environments where fleshy (non-calcareous) macroalgae are dominant primary producers and ecosystem engineers. Few OA studies have focused on the early life stages of large macroalgae such as kelps. This study evaluated the effects of seawater pH on the ontogenic development of meiospores of the native kelp Macrocystis pyrifera and the invasive kelp Undaria pinnatifida, in south-eastern New Zealand. Meiospores of both kelps were released into four seawater pH treatments (pHT 7.20, extreme OA predicted for 2300; pHT 7.65, OA predicted for 2100; pHT 8.01, ambient pH; and pHT 8.40, pre-industrial pH) and cultured for 15 d. Meiospore germination, germling growth rate, and gametophyte size and sex ratio were monitored and measured. Exposure to reduced pHT (7.20 and 7.65) had positive effects on germling growth rate and gametophyte size in both M. pyrifera and U. pinnatifida, whereas, higher pHT (8.01 and 8.40) reduced the gametophyte size in both kelps. Sex ratio of gametophytes of both kelps was biased toward females under all pHT treatments, except for U. pinnatifida at pHT 7.65. Germling growth rate under OA was significantly higher in M. pyrifera compared to U. pinnatifida but gametophyte development was equal for both kelps under all seawater pHT treatments, indicating that the microscopic stages of the native M. pyrifera and the invasive U. pinnatifida will respond similarly to OA.

Seawater pH, and not inorganic nitrogen source, affects pH at the blade surface of Macrocystis pyrifera: implications for responses of the giant kelp to future oceanic conditions.

Ocean acidification (OA), the ongoing decline in seawater pH, is predicted to have wide-ranging effects on marine organisms and ecosystems. For seaweeds, the pH at the thallus surface, within the diffusion boundary layer (DBL), is one of the factors controlling their response to OA. Surface pH is controlled by both the pH of the bulk seawater and by the seaweeds' metabolism: photosynthesis and respiration increase and decrease pH within the DBL (pHDBL ), respectively. However, other metabolic processes, especially the uptake of inorganic nitrogen (Ni ; NO3- and NH4+ ) may also affect the pHDBL . Using Macrocystis pyrifera, we hypothesized that (1) NO3- uptake will increase the pHDBL , whereas NH4+ uptake will decrease it, (2) if NO3- is cotransported with H+ , increases in pHDBL would be greater under an OA treatment (pH = 7.65) than under an ambient treatment (pH = 8.00), and (3) decreases in pHDBL will be smaller at pH 7.65 than at pH 8.00, as higher external [H+ ] might affect the strength of the diffusion gradient. Overall, Ni source did not affect the pHDBL . However, increases in pHDBL were greater at pH 7.65 than at pH 8.00. CO2 uptake was higher at pH 7.65 than at pH 8.00, whereas HCO3- uptake was unaffected by pH. Photosynthesis and respiration control pHDBL rather than Ni uptake. We suggest that under future OA, Macrocystis pyrifera will metabolically modify its surface microenvironment such that the physiological processes of photosynthesis and Ni uptake will not be affected by a reduced pH.

Stress modelling and prediction in presence of scarce data.

OBJECTIVE: Stress at work is a significant occupational health concern. Recent studies have used various sensing modalities to model stress behaviour based on non-obtrusive data obtained from smartphones. However, when the data for a subject is scarce it becomes a challenge to obtain a good model. METHODS: We propose an approach based on a combination of techniques: semi-supervised learning, ensemble methods and transfer learning to build a model of a subject with scarce data. Our approach is based on the comparison of decision trees to select the closest subject for knowledge transfer. RESULTS: We present a real-life, unconstrained study carried out with 30 employees within two organisations. The results show that using information (instances or model) from similar subjects can improve the accuracy of the subjects with scarce data. However, using transfer learning from dissimilar subjects can have a detrimental effect on the accuracy. Our proposed ensemble approach increased the accuracy by ≈10% to 71.58% compared to not using any transfer learning technique. CONCLUSIONS: In contrast to high precision but highly obtrusive sensors, using smartphone sensors for measuring daily behaviours allowed us to quantify behaviour changes, relevant to occupational stress. Furthermore, we have shown that use of transfer learning to select data from close models is a useful approach to improve accuracy in presence of scarce data.

Meiospores produced in sori of nonsporophyllous laminae of Macrocystis pyrifera (Laminariales, Phaeophyceae) may enhance reproductive output.

Different lamina of Macrocystis pyrifera sporophytes (i.e., sporophylls, pneumatocyst-bearing blades, and apical scimitars) in a wave-sheltered site were found to be fertile. We quantified their sorus surface area, reproductive output (number of spores released) and the viability of released spores (germination rate). Sorus area was greatest on the sporophylls, with sporangia developing on >57% of the total area and smallest on the pneumatocyst-bearing blades with 21% of the total area bearing sporangia. The apical scimitar released the greatest number of meiospores (cells · mL(-1)  · cm(-2) ) and the sporophylls the least. Meiospores produced from all types of fertile laminae were equally viable. This reproductive plasticity may enhance reproductive output, and contribute to short and long-distance spore dispersal and the cryptic gametophyte propagule bank for the next generation of sporophytes.

Discovering human immunodeficiency virus mutational pathways using temporal Bayesian networks.

OBJECTIVE: The human immunodeficiency virus (HIV) is one of the fastest evolving organisms in the planet. Its remarkable variation capability makes HIV able to escape from multiple evolutionary forces naturally or artificially acting on it, through the development and selection of adaptive mutations. Although most drug resistance mutations have been well identified, the dynamics and temporal patterns of appearance of these mutations can still be further explored. The use of models to predict mutational pathways as well as temporal patterns of appearance of adaptive mutations could greatly benefit clinical management of individuals under antiretroviral therapy. METHODS AND MATERIAL: We apply a temporal nodes Bayesian network (TNBN) model to data extracted from the Stanford HIV drug resistance database in order to explore the probabilistic relationships between drug resistance mutations and antiretroviral drugs unveiling possible mutational pathways and establishing their probabilistic-temporal sequence of appearance. RESULTS: In a first experiment, we compared the TNBN approach with other models such as static Bayesian networks, dynamic Bayesian networks and association rules. TNBN achieved a 64.2% sparser structure over the static network. In a second experiment, the TNBN model was applied to a dataset associating antiretroviral drugs with mutations developed under different antiretroviral regimes. The learned models captured previously described mutational pathways and associations between antiretroviral drugs and drug resistance mutations. Predictive accuracy reached 90.5%. CONCLUSION: Our results suggest possible applications of TNBN for studying drug-mutation and mutation-mutation networks in the context of antiretroviral therapy, with direct impact on the clinical management of patients under antiretroviral therapy. This opens new horizons for predicting HIV mutational pathways in immune selection with relevance for antiretroviral drug development and therapy plan.

Bacteriostatic anti-Vibrio parahaemolyticus activity of Pseudoalteromonas sp. strains DIT09, DIT44 and DIT46 isolated from Southern Chilean intertidal Perumytilus purpuratus.

We characterised the anti-Vibrio parahaemolyticus (anti-V. parahaemolyticus) marine bacteria DIT09, DIT44 and DIT46 isolated from the intertidal mussel Perumytilus purpuratus. The 16S rRNA gene sequences identify a Pseudoalteromonas sp. that form a clade with P. prydzensis and P. mariniglutinosa. The strains produced bacteriostatic anti-V. parahaemolyticus agents during the exponential growth phase, which were also active against V. cholerae and V. anguillarum, but not on other Gram positive and Gram negative bacteria. Bacteriostatic agents could be permeated by analytic ultra-filtration with 3.5 kDa cut-off, partially precipitated with 70 and 90 % ammonium sulphate, but not extracted with ethyl acetate. Reverse-phase HPLC revealed the production of a set of 5-6 active compounds by each strain (elution from 20 to 40 % acetonitrile), with similar but non identical HPLC patterns. Additionally, V. parahaemolyticus was able to progressively overcome the inhibition of antibiotics in trypticase soy agar with Fe(III) 0.5 up to 2 mM, suggesting the involvement of a set of novel siderophore or active molecules targeted at different Fe-siderophore uptake systems. The overall findings suggest that Pseudoalteromonas sp. DIT strains produce a putatively novel class of bacteriostatic and probably amphiphilic anti-Vibrio agents, indicating the need for further studies with chemical purification followed by their structural and functional characterization. Finally, the crude cell-free extracts, as well as the strains incubated at 10(3) and 10(5) c.f.u./mL, did not cause mortality in Artemia franciscana nauplii, suggesting that these bacteria are serious candidates for further probiotic evaluations with shellfish and fish cultures.

Ruptura isolada da pelve renal secundária ao trauma abdominal contuso / Isolated disruption of the renal pelvis by blunt trauma

Blunt rupture of the renal pelvis is a exceedingly rare injury. Hematuria is absent in one-third of cases. Such injuries are usually caused by desacceleration forces. Despite improved imaging techniques, diagnosis of this injuries is frequently delayed. Diagnosis is suggested by the presence of massive medial extravasation of contrast material at excretory urography or computed tomography. Surgical treatment consists in pyeloplasty or pyeloraphy with stent placement (double J) or nephrostomy.