Degradation and sorption of fipronil and atrazine in Latossols with organic residues from sugarcane crop.

ABSTRACT: Organic residues from sugarcane crop and processing (vinasse, boiler ash, cake filter, and straw) are commonly applied or left on the soil to enhance its fertility. However, they can influence pesticide degradation and sorption. The objective of this study was to assess the effect of adding these organic residues on the degradation and sorption of fipronil and atrazine in two soils of the State of Mato Grosso do Sul, MS, Brazil. The degradation experiment was carried out with laboratory-incubated (40 days; 28°C; 70% field capacity) soils (0-10cm). The batch equilibration method was used to determine sorption. Fipronil (half-life values of 15-105 days) showed to be more persistent than atrazine (7-17 days). Vinasse application to the soil favored fipronil and atrazine degradation, whereas cake filter application decreased the degradation rates for both pesticides. Values for sorption coefficients (Kd) were determined for fipronil (5.1-13.2mL g-1) and atrazine (0.5-1.5mL g-1). Only straw and cake filter residues enhanced fipronil sorption when added to the soil, whereas all sugarcane residues increased atrazine sorption. RESUMO: Resíduos orgânicos do cultivo e processamento da cana-de-açúcar (vinhaça, cinzas, torta de filtro e palha) são usualmente aplicados ou deixados no solo para aumentar sua fertilidade, mas eles podem influenciar na degradação e sorção de agrotóxicos. O objetivo deste estudo foi avaliar o efeito da adição desses resíduos orgânicos no solo sobre a degradação e sorção do fipronil e da atrazina em dois solos no Estado de Mato Grosso do Sul, MS, Brasil. O experimento de degradação foi realizado com solos (0-10cm) incubados em laboratório (40 dias; 28°C; 70% da capacidade de campo). Para determinar a sorção, foi usado o método da batelada. Fipronil mostrou ser mais persistente (valores de meia-vida entre 15-105 dias) que atrazina (7-17 dias). O solo com adição de vinhaça favoreceu a degradação de fipronil e atrazina, enquanto adição da torta de filtro desacelerou o processo. Os valores do coeficiente de sorção (Kd) foram determinados para fipronil (5,1-13,2mL g-1) e atrazina (0,5-1,5mL g-1). Apenas os resíduos palha e torta de filtro aumentaram a sorção de fipronil quando adicionados ao solo, enquanto todos os resíduos aumentaram a sorção de atrazina.

Waste Heat Recovery Systems: Numerical and Experimental Analysis of organic Rankine Cycle Solutions

This thesis aims to present the ORC technology, its advantages and related problems. In particular, it provides an analysis of ORC waste heat recovery system in different and innovative scenarios, focusing on cases from the biggest to the lowest scale. Both industrial and residential ORC applications are considered. In both applications, the installation of a subcritical and recuperated ORC system is examined. Moreover, heat recovery is considered in absence of an intermediate heat transfer circuit. This solution allow to improve the recovery efficiency, but requiring safety precautions. Possible integrations of ORC systems with renewable sources are also presented and investigated to improve the non-programmable source exploitation. In particular, the offshore oil and gas sector has been selected as a promising industrial large-scale ORC application. From the design of ORC systems coupled with Gas Turbines (GTs) as topper systems, the dynamic behavior of the GT+ORC innovative combined cycles has been analyzed by developing a dynamic model of all the considered components. The dynamic behavior is caused by integration with a wind farm. The electric and thermal aspects have been examined to identify the advantages related to the waste heat recovery system installation. Moreover, an experimental test rig has been realized to test the performance of a micro-scale ORC prototype. The prototype recovers heat from a low temperature water stream, available for instance in industrial or residential waste heat. In the test bench, various sensors have been installed, an acquisitions system developed in Labview environment to completely analyze the ORC behavior. Data collected in real time and corresponding to the system dynamic behavior have been used to evaluate the system performance based on selected indexes. Moreover, various operational steady-state conditions are identified and operation maps are realized for a completely characterization of the system and to detect the optimal operating conditions.

Experimental Project on the Safety and the Optimization of the Use of Glyphosate-Based Herbicides in the Grain Sector.

INTRODUCTION: Glyphosate is the most widely applied pesticide worldwide and it is an active ingredient of all glyphosate-based herbicides (GBHs), including in the formulation “Roundup” . It is unclear if the glyphosate present in ground water can be absorbed and translocated in different parts of the pants, particularly wheat plants. This indeed represents an important aspect for productivity (being this a powerful herbicide) and organic certification of the products (the use of glyphosate is not admitted in organic farming and the ubiquitous contamination of glyphosate in water might in theory affect the level of glyphosate in the plants). Overall, epidemiological, in vivo and in vitro studies available in literature present conflicting findings on the safety of glyphosate. METHODS: The work performed for this PhD thesis aimed to experimentally test the root absorption and the eventual translocation of the glyphosate herbicide in the different parts of the wheat plant (Triticum durum) starting from ground water. Furthermore we aimed to experimentally test the effects of the exposure to GBHs at doses of glyphosate considered to be “safe”, the US ADI of 1.75 mg/kg bw/day, defined as the chronic Reference Dose (cRfD) determined by the US EPA, in in vivo models (Sprague-Dawley rats) and in vitro models (Caco2 and L929). RESULTS: All the experimental absorption studies on wheat plants performed have given negative results in terms of the presence of glyphosate or AMPA in the grain of durum wheat. On the other hand the experimental safety studies on in vitro and in vivo models highlighted different effects at doses currently considered safe for humans and with no effects in animals. CONCLUSION: Overall the integration of the findings from absorption in plants and safety studies will serve as solid evidence-base for risk assessment and productive strategies for agriculture.

Identification of sunflower genotypes suitable for organic agriculture and development of analytical tools for their traceability

Thanks to the development and combination of molecular markers for the genetic traceability of sunflower varieties and a gas chromatographic method for the determination of the FAs composition of sunflower oil, it was possible to implement an experimental method for the verification of both the traceability and the variety of organic sunflower marketed by Agricola Grains S.p.A. The experimental activity focused on two objectives: the implementation of molecular markers for the routine control of raw material deliveries for oil extraction and the improvement and validation of a gas chromatographic method for the determination of the FAs composition of sunflower oil. With regard to variety verification and traceability, the marker systems evaluated were the following: SSR markers (12) arranged in two multiplex sets and SCAR markers for the verification of cytoplasmic male sterility (Pet1) and fertility. In addition, two objectives were pursued in order to enable a routine application in the industrial field: the development of a suitable protocol for DNA extraction from single seeds and the implementation of a semi-automatic capillary electrophoresis system for the analysis of marker fragments. The development and validation of a new GC/FID analytical method for the determination of fatty acids (FAME) in sunflower achenes to improve the quality and efficiency of the analytical flow in the control of raw and refined materials entering the Agricola Grains S.p.A. production chain. The analytical performances being validated by the newly implemented method are: linearity of response, limit of quantification, specificity, precision, intra-laboratory precision, robustness, BIAS. These parameters are used to compare the newly developed method with the one considered as reference - Commission Regulation No. 2568/91 and Commission Implementing Regulation No. 2015/1833. Using the combination of the analytical methods mentioned above, the documentary traceability of the product can be confirmed experimentally, providing relevant information for subsequent marketing.

Chemiluminescence – based bioanalytical devices for astrobiological, food safety and clinical applications

At the intersection of biology, chemistry, and engineering, biosensors are a multidisciplinary innovation that provide a cost-effective alternative to traditional laboratory techniques. Due to their advantages, biosensors are used in medical diagnostics, environmental monitoring, food safety and many other fields. The first part of the thesis is concerned with learning the state of the art of paper-based immunosensors with bioluminescent (BL) and chemiluminescent (CL) detection. The use of biospecific assays combined with CL detection and paper-based technology offers an optimal approach to creating analytical tools for on-site applications and we have focused on the specific areas that need to be considered more in order to ensure a future practical implementation of these methods in routine analyses. The subsequent part of the thesis addresses the development of an autonomous lab-on-chip platform for performing chemiluminescent-based bioassays in space environment, exploiting a CubeSat platform for astrobiological investigations. An origami-inspired microfluidic paper-based analytical device has been developed with the purpose of assesses its performance in space and to evaluate its functionality and the resilience of the (bio)molecules when exposed to a radiation-rich environment. Subsequently, we designed a paper-based assay to detect traces of ovalbumin in food samples, creating a user-friendly immunosensing platform. To this purpose, we developed an origami device that exploits a competitive immunoassay coupled with chemiluminescence detection and magnetic microbeads used to immobilize ovalbumin on paper. Finally, with the aim of exploring the use of biomimetic materials, an hydrogel-based chemiluminescence biosensor for the detection of H2O2 and glucose was developed. A guanosine hydrogel was prepared and loaded with luminol and hemin, miming a DNAzyme activity. Subsequently, the hydrogel was modified by incorporating glucose oxidase enzyme to enable glucose biosensing. The emitted photons were detected using a portable device equipped with a smartphone's CMOS (complementary metal oxide semiconductor) camera for CL emission detection.

Predictive Value Of Phase I Trials For Safety In Later Trials And Final Approved Dose: Analysis Of 61 Approved Cancer Drugs.

Phase I trials use a small number of patients to define a maximum tolerated dose (MTD) and the safety of new agents. We compared data from phase I and registration trials to determine whether early trials predicted later safety and final dose. We searched the U.S. Food and Drug Administration (FDA) website for drugs approved in nonpediatric cancers (January 1990-October 2012). The recommended phase II dose (R2PD) and toxicities from phase I were compared with doses and safety in later trials. In 62 of 85 (73%) matched trials, the dose from the later trial was within 20% of the RP2D. In a multivariable analysis, phase I trials of targeted agents were less predictive of the final approved dose (OR, 0.2 for adopting ± 20% of the RP2D for targeted vs. other classes; P = 0.025). Of the 530 clinically relevant toxicities in later trials, 70% (n = 374) were described in phase I. A significant relationship (P = 0.0032) between increasing the number of patients in phase I (up to 60) and the ability to describe future clinically relevant toxicities was observed. Among 28,505 patients in later trials, the death rate that was related to drug was 1.41%. In conclusion, dosing based on phase I trials was associated with a low toxicity-related death rate in later trials. The ability to predict relevant toxicities correlates with the number of patients on the initial phase I trial. The final dose approved was within 20% of the RP2D in 73% of assessed trials.

[between The Country And The Laboratory: The Dynamics Of The Production Of Knowledge At The Menopause Outpatients Clinic At Caism, Unicamp.]

This study investigates the practices involved in the production of knowledge about menopause at Caism, Unicamp, a reference center for public policies for women's health. Gynecological appointments and psychological support meetings were observed, and women and doctors were interviewed in order to identify what discourse circulates there and how different actors are brought in to ensure that the knowledge produced attains credibility and travels beyond the boundaries of the teaching hospital to become universal. The analysis is based on localized studies aligned with social studies of science and technology.

[between The Country And The Laboratory: The Dynamics Of The Production Of Knowledge At The Menopause Outpatients Clinic At Caism, Unicamp].

This study investigates the practices involved in the production of knowledge about menopause at Caism, Unicamp, a reference center for public policies for women's health. Gynecological appointments and psychological support meetings were observed, and women and doctors were interviewed in order to identify what discourse circulates there and how different actors are brought in to ensure that the knowledge produced attains credibility and travels beyond the boundaries of the teaching hospital to become universal. The analysis is based on localized studies aligned with social studies of science and technology.

Efficacy And Safety Of Intravitreal Bevacizumab In Eyes With Neovascular Glaucoma Undergoing Ahmed Glaucoma Valve Implantation: 2-year Follow-up.

To evaluate the efficacy and safety of intravitreal bevacizumab (IVB) in eyes with neovascular glaucoma (NVG) undergoing Ahmed glaucoma valve (AGV) implantation. This was a multicentre, prospective, randomized clinical trial that enrolled 40 patients with uncontrolled neovascular glaucoma that had undergone panretinal photocoagulation and required glaucoma drainage device implantation. Patients were randomized to receive IVB (1.25 mg) or not during Ahmed valve implant surgery. Injections were administered intra-operatively, and 4 and 8 weeks after surgery. After a mean follow-up of 2.25 ± 0.67 years (range 1.5-3 years), both groups showed a significant decrease in IOP (p < 0.05). There was no difference in IOP between groups except at the 18-month interval, when IOP in IVB group was significantly lower (14.57 ± 1.72 mmHg vs. 18.37 ± 1.06 mmHg - p = 0.0002). There was no difference in survival success rates between groups. At 24 months, there was a trend to patients treated with IVB using less antiglaucoma medications than the control group (p = 0.0648). Complete regression of rubeosis iridis was significantly more frequent in the IVB group (80%) than in the control group (25%) (p = 0.0015). Intravitreal bevacizumab may lead to regression of new vessels both in the iris and in the anterior chamber angle in patients with neovascular glaucoma undergoing Ahmed glaucoma valve implantation. There is a trend to slightly lower IOPs and number of medications with IVB use during AGV implantation for neovascular glaucoma.

Long-term Efficacy And Safety Of Tenofovir Disoproxil Fumarate In Hiv-1-infected Adolescents Failing Antiretroviral Therapy: The Final Results Of Study Gs-us-104-0321.

Reports of long-term tenofovir disoproxil fumarate (TDF) treatment in HIV-infected adolescents are limited. We present final results from the open-label (OL) TDF extension following the randomized, placebo (PBO)-controlled, double-blind phase of GS-US-104-0321 (Study 321). HIV-infected 12- to 17-year-olds treated with TDF 300 mg or PBO with an optimized background regimen (OBR) for 24-48 weeks subsequently received OL TDF plus OBR in a single arm study extension. HIV-1 RNA and safety, including bone mineral density (BMD), was assessed in all TDF recipients. Eighty-one subjects received TDF (median duration 96 weeks). No subject died or discontinued OL TDF for safety/tolerability. At week 144, proportions with HIV-1 RNA <50 copies/mL were 30.4% (7 of 23 subjects with baseline HIV-1 RNA >1000 c/mL initially randomized to TDF), 41.7% (5 of 12 subjects with HIV-1 RNA <1000 c/mL who switched PBO to TDF) and 0% (0 of 2 subjects failed randomized PBO plus OBR with HIV-1 RNA >1000 c/mL and switched PBO to TDF). Viral resistance to TDF occurred in 1 subject. At week 144, median decrease in estimated glomerular filtration rate was 38.1 mL/min/1.73 m (n = 25). Increases in median spine (+12.70%, n = 26) and total body less head BMD (+4.32%, n = 26) and height-age adjusted Z-scores (n = 21; +0.457 for spine, +0.152 for total body less head) were observed at week 144. Five of 81 subjects (6%) had persistent >4% BMD decreases from baseline. Some subjects had virologic responses to TDF plus OBR, and TDF resistance was rare. TDF was well tolerated and can be considered for treatment of HIV-infected adolescents.

Human Herpesvirus Infections Of The Central Nervous System: Laboratory Diagnosis Based On Dna Detection By Nested Pcr In Plasma And Cerebrospinal Fluid Samples.

Infections of the central nervous systems (CNS) present a diagnostic problem for which an accurate laboratory diagnosis is essential. Invasive practices, such as cerebral biopsy, have been replaced by obtaining a polymerase chain reaction (PCR) diagnosis using cerebral spinal fluid (CSF) as a reference method. Tests on DNA extracted from plasma are noninvasive, thus avoiding all of the collateral effects and patient risks associated with CSF collection. This study aimed to determine whether plasma can replace CSF in nested PCR analysis for the detection of CNS human herpesvirus (HHV) diseases by analysing the proportion of patients whose CSF nested PCR results were positive for CNS HHV who also had the same organism identified by plasma nested PCR. In this study, CSF DNA was used as the gold standard, and nested PCR was performed on both types of samples. Fifty-two patients with symptoms of nervous system infection were submitted to CSF and blood collection. For the eight HHV, one positive DNA result-in plasma and/or CSF nested PCR-was considered an active HHV infection, whereas the occurrence of two or more HHVs in the same sample was considered a coinfection. HHV infections were positively detected in 27/52 (51.9%) of the CSF and in 32/52 (61.5%) of the plasma, difference not significant, thus nested PCR can be performed on plasma instead of CSF. In conclusion, this findings suggest that plasma as a useful material for the diagnosis of cases where there is any difficulty to perform a CSF puncture.

Engineered Nanoparticles And Organic Matter: A Review Of The State-of-the-art.

Growth in the development and production of engineered nanoparticles (ENPs) in recent years has increased the potential for interactions of these nanomaterials with aquatic and terrestrial environments. Carefully designed studies are therefore required in order to understand the fate, transport, stability, and toxicity of nanoparticles. Natural organic matter (NOM), such as the humic substances found in water, sediment, and soil, is one of the substances capable of interacting with ENPs. This review presents the findings of studies of the interaction of ENPs and NOM, and the possible effects on nanoparticle stability and the toxicity of these materials in the environment. In addition, ENPs and NOM are utilized for many different purposes, including the removal of metals and organic compounds from effluents, and the development of new electronic sensors and other devices for the detection of active substances. Discussion is therefore provided of some of the ways in which NOM can be used in the production of nanoparticles. Although there has been an increase in the number of studies in this area, further progress is needed to improve understanding of the dynamic interactions between ENPs and NOM.

The Influence Of The Buffering Capacity On The Production Of Organic Acids And Alcohols From Wastewater In Anaerobic Reactor.

Some bacteria common in anaerobic digestion process can ferment a broad variety of organic compounds to organic acids, alcohols, and hydrogen, which can be used as biofuels. Researches are necessary to control the microbial interactions in favor of the alcohol production, as intermediary products of the anaerobic digestion of organic compounds. This paper reports on the effect of buffering capacity on the production of organic acids and alcohols from wastewater by a natural mixed bacterial culture. The hypothesis tested was that the increase of the buffering capacity by supplementation of sodium bicarbonate in the influent results in benefits for alcohol production by anaerobic fermentation of wastewater. When the influent was not supplemented with sodium bicarbonate, the chemical oxygen demand (COD)-ethanol and COD-methanol detected in the effluent corresponded to 22.5 and 12.7 % of the COD-sucrose consumed. Otherwise, when the reactor was fed with influent containing 0.5 g/L of sodium bicarbonate, the COD-ethanol and COD-methanol were effluents that corresponded to 39.2 and 29.6 % of the COD-sucrose consumed. Therefore, the alcohol production by supplementation of the influent with sodium bicarbonate was 33.6 % higher than the fermentation of the influent without sodium bicarbonate.

Resolução do ibuprofeno: um projeto para disciplina de química orgânica experimental

A practical and didactic sequence of experiments was proposed to illustrate the stereochemistry concept, optically active compounds, resolution of racemates, and use of the NMR technique, including 2D-COSY for identification of organic compounds, on a laboratory course for undergraduate students. The sequence was: extractions of racemic ibuprofen and chiral naproxen from commercial tablets; syntheses of diastereoisomeric amides reacting chiral (S)-(-)-α-methylbenzylamine with (±)-ibuprofen; separation and determination of absolute configuration of amides by ¹H NMR spectroscopy and GC analysis, and hydrolysis of amides to obtain (+)- and (-)-ibuprofen.