Specificity and selectivity improvement in doping analysis using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry

Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry was used for the identification of forty doping agents. The improvement in the specificity was remarkable, allowing the resolution of analytes that could not be done by one-dimensional chromatographic systems. The sensitivity observed for different classes of prohibited substances was clearly below the value required by the World Anti-Doping Agency. In addition time-of-flight mass spectrometry gives full spectrum for all analytes without any interference from the matrix, resulting in selectivity improvements. These results could support the implementation of an exhaustive monitoring approach for hundreds of doping agents in a single injection.

DEVELOPMENT AND VALIDATION OF ANALYTICAL METHOD FOR PALM OIL DETERMINATION IN MICROCAPSULES PRODUCED BY COMPLEX COACERVATION

The microencapsulation of palm oil may be a mechanism for protecting and promoting the controlled release of its bioactive compounds. To optimize the microencapsulation process, it is necessary to accurately quantify the palm oil present both external and internal to the microcapsules. In this study, we developed and validated a spectrophotometric method to determine the microencapsulation efficiency of palm oil by complex coacervation. We used gelatin and gum arabic (1:1) as wall material in a 5% concentration (w/v) and palm oil in the same concentration. The coacervates were obtained at pH 4.0 ± 0.01, decanted for 24 h, frozen (−40 ºC), and lyophilized for 72 h. Morphological analyzes were then performed. We standardized the extraction of the external palm oil through five successive washes with an organic solvent. We then explored the best method for rupturing the microcapsules. After successive extractions with hexane, we determined the amount of palm oil contained in the microcapsules using a spectrophotometer. The proposed method was shown to be of low cost, fast, and easy to implement. In addition, in the validation step, we confirmed the method to be safe and reliable, as it proved to be specific, accurate, precise, and robust.

The effect of the birth hospital and the time of birth on the outcome of Finnish very preterm infants

The purpose of this study was to evaluate the effect of the birth hospital and the time of birth on mortality and the long-term outcome of Finnish very low birth weight (VLBW) or very low gestational age (VLGA) infants. This study included all Finnish VLBW/VLGA infants born at <32 gestational weeks or with a birth weight of ≤1500g, and controls born full-term and healthy. In the first part of the study, the mortality of VLBW/VLGA infants born in 2000–2003 was studied. The second part of the study consisted of a five-year follow-up of VLBW/VLGA infants born in 2001–2002. The study was performed using data from parental questionnaires and several registers. The one-year mortality rate was 11% for live-born VLBW/VLGA infants, 22% for live-born and stillborn VLBW/VLGA infants, and 0% for the controls. In live-born and in all (including stillbirths) VLBW/VLGA infants, the adjusted mortality was lower among those born in level III hospitals compared with level II hospitals. Mortality rates of live-born VLBW/VLGA infants differed according to the university hospital district where the birth hospital was located, but there were no differences in mortality between the districts when stillborn infants were included. There was a trend towards lower mortality rates in VLBW/VLGA infants born during office hours compared with those born outside office hours (night time, weekends, and public holidays). When stillborn infants were included, this difference according to the time of birth was significant. Among five-year-old VLBW/VLGA children, morbidity, use of health care resources, and problems in behaviour and development were more common in comparison with the controls. The health-related quality of life of the surviving VLBW/VLGA children was good but, statistically, it was significantly lower than among the controls. The median and the mean number of quality-adjusted life-years were 4.6 and 3.6 out of a maximum five years for all VLBW/VLGA children. For the controls, the median was 4.8 and the mean was 4.9. Morbidity rates, the use of health care resources, and the mean quality-adjusted life-years differed for VLBW/VLGA children according to the university hospital district of birth. However, the time of birth, the birth hospital level or university hospital district were not associated with the health-related quality of life, nor with behavioural and developmental scores of the survivors at the age of five years. In conclusion, the decreased mortality in level III hospitals was not gained at the expense of long-term problems. The results indicate that VLBW/VLGA deliveries should be centralized to level III hospitals and the regional differences in the treatment practices should further be clarified. A long-term follow-up on the outcome of VLBW/VLGA infants is important in order to recognize the critical periods of care and to optimise the care. In the future, quality-adjusted life-years can be used as a uniform measure for comparing the effectiveness of care between VLBW/VLGA infants and different patient groups

Development and validation of spectrophotometric method for the determination of DPP-4 inhibitor, sitagliptin, in its pharmaceutical preparations

A simple, sensitive and reproducible spectrophotometric method was developed for the determination of sitagliptin phosphate in bulk and in pharmaceutical formulations. The proposed method is based on condensation of the primary amino group of sitagliptin phosphate with acetyl acetone and formaldehyde producing a yellow colored product, which is measured spectrophotometrically at 430nm. The color was stable for about 1 hour. Beer's law is obeyed over a concentration range of 5-25 µg/ml. The apparent molar absorptivity and Sandell sensitivity values are 1.067 x 10(4) Lmol-1cm-1 and 0.0471 µgcm-2 respectively. All the variables were studied to optimize the reaction conditions. No interference was observed in the presence of common pharmaceutical excipients. The validity of the method was tested by analyzing sitagliptin phosphate in its pharmaceutical preparations. Good recoveries were obtained. The developed method was successfully employed for the determination of sitagliptin phosphate in various pharmaceutical preparations.

Desiccation time of the spring sorghum as a predecessor crop for summer soybean and autumn bean in a no-tillage system

ABSTRACT Several authors have been questioned the desiccation interval between the coverage plants and sowing plants for the soybean crop. Therefore, this study aimed to evaluate the desiccation time of the spring sorghum as a predecessor crop for summer soybean and then for autumn bean, focusing on the straw formation for maintenance of the no-tillage system and to evaluate the yield of soybeans and beans grain, as well as analyzing the interference of sorghum straw in these cultures. The experiment was developed in the Teaching and Research Farm of FE/UNESP located in Ilha Solteira/SP where it was used an experimental design of randomized blocks with five treatments and six repetitions. The treatments consisted of five different intervals between sorghum desiccation and soybean sowing (being with D7 - Drying sorghum seven days before the soybean sowing; and successively for D14, D21, D28 and D35). In order to analyze the results, it was used the Tukey test for a 10% level of significance and the statistical program called Sisvar. The "Cober Crop" sorghum exerted influence on soybean yield but this effect was not lasting for the bean crop in succession to the soybeans.

Follicle and corpus luteum size and vascularity as predictors of fertility at the time of artificial insemination and embryo transfer in beef cattle

Abstract:Two ultrasound based fertility prediction methods were tested prior to embryo transfer (ET) and artificial insemination (AI) in cattle. Female bovines were submitted to estrous synchronization prior to ET and AI. Animals were scanned immediately before ET and AI procedure to target follicle and corpus luteum (CL) size and vascularity. In addition, inseminated animals were also scanned eleven days after insemination to target CL size and vascularity. All data was compared with fertility by using gestational diagnosis 35 days after ovulation. Prior to ET, CL vascularity showed a positive correlation with fertility, and no pregnancy occurred in animals with less than 40% of CL vascularity. Prior to AI and also eleven days after AI, no relationship with fertility was seen in all parameters analyzed (follicle and CL size and vascularity), and contrary, cows with CL vascularity greater than 70% exhibit lower fertility. In inseminated animals, follicle size and vascularity was positive related with CL size and vascularity, as shown by the presence of greater CL size and vascularity originated from follicle with also greater size and vascularity. This is the first time that ultrasound based fertility prediction methods were tested prior to ET and AI and showed an application in ET, but not in AI programs. Further studies are needed including hormone profile evaluation to improve conclusion.

Adaptation of TRIZ Method for Problem Solving in Process Engineering

TRIZ is one of the well-known tools, based on analytical methods for creative problem solving. This thesis suggests adapted version of contradiction matrix, a powerful tool of TRIZ and few principles based on concept of original TRIZ. It is believed that the proposed version would aid in problem solving, especially those encountered in chemical process industries with unit operations. In addition, this thesis would help fresh process engineers to recognize importance of various available methods for creative problem solving and learn TRIZ method of creative problem solving. This thesis work mainly provides idea on how to modify TRIZ based method according to ones requirements to fit in particular niche area and solve problems efficiently in creative way. Here in this case, the contradiction matrix developed is based on review of common problems encountered in chemical process industry, particularly in unit operations and resolutions are based on approaches used in past to handle those issues.

Floristic and structural variation of weeds in eucalyptus plantations as influenced by relief and time of year

The objective of this work was to analyze the floristic variation and phytosociological structure of weeds as influenced by relief and time of year in eucalyptus plantations in Santana do Paraíso and Guanhães - MG. The total area sampled for each locality was approximately 10 ± 3 hectares, comprising three types of relief: lowland, slope, and upper area. In each type of relief, 10 plots of 1 m² were sampled, corresponding to 30 plots per locality, where they were randomly allocated in a zigzag. The taxonomic identification was performed in four assessments, corresponding to the months of November and March, comprising two ratings each season, always at the same points, and geo-referenced using the Global Positioning System (GPS). A total of 3,893 individuals, 18 families and 61 species, were identified in Santana do Paraiso and a total of 1,166 individuals, 13 families and 58 species, in Guanhães. In both localities, the most representative families in terms of wealth were: Poaceae, Asteraceae, and Fabaceae. Galinsoga parviflora was the most abundant species. The Vernonia polyantes was identified only in the lowlands, while Arrabida florida was identified in the slope and upper area. On the other hand, Emilia coccinea, Sida rhombifolia, S. paniculatum and Spermacoce latifolia were common to all three environments. Commelina benghalensis was present only in the month of March, while G. parviflora was present only in the month of November. It was concluded that the floristic and phytosociological variation of weeds in eucalyptus plantations is influenced by the type of relief and time of year, which should guide the management practices used in the culture.

Effects of irrigated rice sowing season and imazapyr + imazapic time of application on rice grain yield and red rice management

Irrigated rice sowing season and red rice competition are among the main factors affecting grain yield. The objective of this work was to evaluate the sowing date of irrigated rice and moments of application of the herbicide imazapyr + imazapic to control red rice management and irrigated rice grain yield. Eight experiments were performed at the following dates (09/30, 10/19, 11/08 and 12/01) for the 2010/2011 harvest season and (09/27, 10/17, 11/08 and 12/05) for the 2011/2012 harvest season. The treatments were: application of the herbicide imazapyr + imazapic at doses of 105+35 g ha-1 in pre-emergence (PRE); 52.5+17.5 g ha‑1 in pre-emergence and 52.5+17.5 g ha-1 in post-emergence (PRE + POST); and 105+35 g ha-1 in post- emergence (POST), and a control without application and no weeding. The cultivar Puitá Inta CL was used and a randomized block design with four replicates. A joint analysis of the experiments was carried out. There was less emergence of red rice and higher grain yield of the irrigated rice at the early periods (09/30/10 and 09/27/11), with 10,578 and 8,653 kg ha-1, respectively. At the end of the season (12/01/10 and 12/05/11), there was greater reduction of the red rice seed bank. Sowing at the beginning of the recommended period provided more irrigated rice grain yield. The application of imazapyr + imazapic at a dose of 52.5+17.5 g ha-1 in PRE + 52.5+17.5 g ha-1 POST, and 105+35 g ha-1 only in PRE and POST was effective in the control of red rice.

INFLUENCE OF THE GLYPHOSATE FORMULATIONS ON WETTABILITY AND EVAPORATION TIME OF DROPLETS ON DIFFERENT TARGETS

ABSTRACTEfficiency of weed control can be increased if the herbicide formulation provides higher target coverage and evaporation time that enable an adequate distribution of herbicide on the target plant, allowing the absorption to continue even after the droplets evaporation. The aim of this research was to assess the influence of glyphosate formulations on the wetted area and evaporation time of droplets on different targets. Tests were conducted with droplets sizing from 500 μm containing three formulations of glyphosate (isopropylamine salt, ammonium salt and potassium salt) deposited on three surfaces, two leaves (Bidens pilosa and Cenchrus echinatus) and glass slides. Sequential images analyses were used to quantify the evaporation time and the wetted area. An experimental system was utilized that was composed of a droplet generator, a stereo microscope with a camera to capture images, as well as an environmental chamber controlled for temperature and relative humidity. The kind of glyphosate formulations and target surfaces are crucial in the wetted area and evaporation time. The isopropylamine salt decreased the wetted area and evaporation time when compared with ammonium salt and potassium salt for all the surfaces deposited on. Bidens pilosa allows an increased wetted area for all the glyphosate formulations when compared to Cenchrus echinatus and glass slides.

Inulin production by Vernonia herbacea as influenced by mineral fertilization and time of harvest

The underground organs of Vernonia herbacea (Vell.) Rusby, known as rhizophores, acumulate 80% of their dry mass as fructans of the inulin type. In view of the growing industrial use of fructans as dietetic and general food products, and of their medical application, the present investigation aimed at evaluating the effect of mineral fertilization and period of cultivation on the production of these carbohydrates in field trials. Plants used in the experiments were obtained by vegetative propagation from rhizophores collected from plants growing in natural areas of the cerrado, and cultivated for two years. Fertilization consisted of N:P2O5:K2O (80:200:150 kg.ha-1) plus 80 kg.ha-1 nitrogen as dressing. Soil fertilization did not stimulate biomass or inulin production, but in the second year of cultivation a dramatic gain in biomass and inulin was detected in both treated and control plants. Inulin production varied from 113 to 674 kg.ha-1 which corresponds to 43% of the rhizophore dry mass. The composition of fructans was not altered by fertilization, although treated plants had a higher proportion of sucrose and fructans with degree of polymerization 3-8 in the second year of cultivation. The results identify this species as a fructan source similar to other commercial crops and recommend further agronomic studies, aimed at increasing the production of this polysaccharide.

The Roman Empire as it was in the time of Julius Caesar and it is described in his Commentaries, and in Silius Italicus

Julkaisussa: Geographia classica : the geography of the ancients

Purification of human albumin by the combination of the method of Cohn with liquid chromatography

Large volumes of plasma can be fractionated by the method of Cohn at low cost. However, liquid chromatography is superior in terms of the quality of the product obtained. In order to combine the advantages of each method, we developed an integrated method for the production of human albumin and immunoglobulin G (IgG). The cryoprecipitate was first removed from plasma for the production of factor VIII and the supernatant of the cryoprecipitate was fractionated by the method of Cohn. The first precipitate, containing fractions (F)-I + II + III, was used for the production of IgG by the chromatographic method (see Tanaka K et al. (1998) Brazilian Journal of Medical and Biological Research, 31: 1375-1381). The supernatant of F-I + II + III was submitted to a second precipitation and F-IV was obtained and discarded. Albumin was obtained from the supernatant of the precipitate F-IV by liquid chromatography, ion-exchange on DEAE-Sepharose FF, filtration through Sephacryl S-200 HR and introduction of heat treatment for fatty acid precipitation. Viral inactivation was performed by pasteurization at 60ºC for 10 h. The albumin product obtained by the proposed procedure was more than 99% pure for the 15 lots of albumin produced, with a mean yield of 25.0 ± 0.5 g/l plasma, containing 99.0 to 99.3% monomer, 0.7 to 1.0% dimers, and no polymers. Prekallikrein activator levels were <=5 IU/ml. This product satisfies the requirements of the 1997 Pharmacopée Européenne.

Changes in clinical and laboratory findings at the time of diagnosis of primary hyperparathyroidism in a University Hospital in São Paulo from 1985 to 2002

In contrast to most developed countries, most patients with primary hyperparathyroidism in Brazil are still symptomatic at diagnosis. However, we have been observing a change in this pattern, especially in the last few years. We evaluated 104 patients, 77 females and 27 males aged 11-79 years (mean: 54.4 years), diagnosed between 1985 and 2002 at a University Hospital. Diagnosis was made on the basis of clinical findings and of high total and/or ionized calcium levels, high or inappropriate levels of intact parathyroid hormone and of surgical findings in 80 patients. Patients were divided into three groups, i.e., patients diagnosed from 1985 to 1989, patients diagnosed from 1990 to 1994, and patients diagnosed from 1995 to 2002. The number of new cases diagnosed/year increased from 1.8/year in the first group to 6.0/year in the second group and 8.1/year in the third group. The first group comprised 9 patients (mean serum calcium ± SD, 13.6 ± 1.6 mg/dl), 8 of them (88.8%) defined as symptomatic. The second group comprised 30 patients (mean calcium ± SD, 12.2 ± 1.63 mg/dl), 22 of them defined as symptomatic (73.3%). The third group contained 65 patients (mean calcium 11.7 ± 1.1 mg/dl), 34 of them symptomatic (52.3%). Patients from the first group tended to be younger (mean ± SD, 43.0 ± 15 vs 55.1 ± 14.4 and 55.7 ± 17.3 years, respectively) and their mean serum calcium was significantly higher (P < 0.05). All of symptomatic patients independent of group had higher serum calcium levels (12.4 ± 1.53 mg/dl, N = 64) than asymptomatic patients (11.4 ± 1.0 mg/dl, N = 40). Our data showed an increase in the percentage of asymptomatic patients over the years in the number of primary hyperparathyroidism cases diagnosed. This finding may be due to an increased availability of diagnostic methods and/or to an increased awareness about the disease.

Effect of the time-of-day of training on explicit memory

Studies have shown a time-of-day of training effect on long-term explicit memory with a greater effect being shown in the afternoon than in the morning. However, these studies did not control the chronotype variable. Therefore, the purpose of this study was to assess if the time-of-day effect on explicit memory would continue if this variable were controlled, in addition to identifying the occurrence of a possible synchronic effect. A total of 68 undergraduates were classified as morning, intermediate, or afternoon types. The subjects listened to a list of 10 words during the training phase and immediately performed a recognition task, a procedure which they repeated twice. One week later, they underwent an unannounced recognition test. The target list and the distractor words were the same in all series. The subjects were allocated to two groups according to acquisition time: a morning group (N = 32), and an afternoon group (N = 36). One week later, some of the subjects in each of these groups were subjected to a test in the morning (N = 35) or in the afternoon (N = 33). The groups had similar chronotypes. Long-term explicit memory performance was not affected by test time-of-day or by chronotype. However, there was a training time-of-day effect [F (1,56) = 53.667; P = 0.009] with better performance for those who trained in the afternoon. Our data indicated that the advantage of training in the afternoon for long-term memory performance does not depend on chronotype and also that this performance is not affected by the synchronic effect.