Preparação de N-alquil derivados do 1-bromo-2,4-dinitrobenzeno e do 1-cloro-2-nitrobenzeno: Uma alternativa às aulas práticas de substituição nucleofílica aromática

Preparation of the title compounds are described as an alternative nucleophilic aromatic substitution for practices in the graduate laboratory. The low toxicity and disponibility of the reagents make a suitable procedure approach to experiments regarding this aromatic reaction.

UM MÉTODO EFICIENTE PARA A OBTENÇÃO DE DERIVADOS DE 1-ALQUILAMINO-2,4-DINITROBENZENO E A REDUÇÃO REGIOSSELETIVA PARA A OBTENÇÃO DE DERIVADOS DE 1-ALQUILAMINO-2-AMINO-4-NITROBENZENO

Both primary and secondary amines react with 2,4-dinitrochlorobenzene to give derivatives of 1-alkylamino-2,4-dinitrobenzene. These compounds are important intermediates for the synthesis of a diverse range of products. The methodology reported in the present study involves either the room temperature reaction or heating at 70 °C in ethanol in the presence of triethylamine. This transformation occurs via a nucleophilic substitution reaction. The 1-alkylamino-2,4-dinitrobenzene derivatives were obtained in greater than 90% purified yield. The selective reduction of dinitro compounds is an important synthetic strategy for the synthesis of intermediates for dyes, pharmaceuticals and agrochemicals. The use of SnCl2 as a suspension in EtOAc is a promising method for the regio- and chemo-selective reduction of 1-alkylamino-2,4-dinitrobenzenes to 1-alkylamino-2-amino-4-nitrobenzenes. These products are useful intermediates in organic synthesis.

2-Bromo-1,4-naphthoquinone: a potentially improved substitute of menadione in Apatone™ therapy

Apatone™, a combination of menadione (2-methyl-1,4-naphthoquinone, VK3) and ascorbic acid (vitamin C, VC) is a new strategy for cancer treatment. Part of its effect on tumor cells is related to the cellular pro-oxidative imbalance provoked by the generation of hydrogen peroxide (H2O2) through naphthoquinone redox cycling. In this study, we attempted to find new naphthoquinone derivatives that would increase the efficiency of H2O2 production, thereby potentially increasing its efficacy for cancer treatment. The presence of an electron-withdrawing group in the naphthoquinone moiety had a direct effect on the efficiency of H2O2 production. The compound 2-bromo-1,4-naphthoquinone (BrQ), in which the bromine atom substituted the methyl group in VK3, was approximately 10- and 19-fold more efficient than VK3 in terms of oxygen consumption and H2O2 production, respectively. The ratio [H2O2]produced / [naphthoquinone]consumed was 68 ± 11 and 5.8 ± 0.2 (µM/µM) for BrQ and VK3, respectively, indicating a higher efficacy of BrQ as a catalyst for the autoxidation of ascorbic acid. Both VK3 and BrQ reacted with glutathione (GSH), but BrQ was the more effective substrate. Part of GSH was incorporated into the naphthoquinone, producing a nucleophilic substitution product (Q-SG). The depletion of BrQ by GSH did not prevent its redox capacity since Q-SG was also able to catalyze the production of reactive oxygen species. VK3/VC has already been submitted to clinical trials for the treatment of prostate cancer and has demonstrated promising results. However, replacement of VK3 with BrQ will open new lines of investigation regarding this approach to cancer treatment.

Impact of Light Salt Substitution for Regular Salt on Blood Pressure of Hypertensive Patients

Background: Studies have shown sodium restriction to have a beneficial effect on blood pressure (BP) of hypertensive patients. Objective: To evaluate the impact of light salt substitution for regular salt on BP of hypertensive patients. Methods: Uncontrolled hypertensive patients of both sexes, 20 to 65 years-old, on stable doses of antihypertensive drugs were randomized into Intervention Group (IG - receiving light salt) and Control Group (CG - receiving regular salt). Systolic BP (SBP) and diastolic BP (DBP) were analyzed by using casual BP measurements and Home Blood Pressure Monitoring (HBPM), and sodium and potassium excretion was assessed on 24-hour urine samples. The patients received 3 g of salt for daily consumption for 4 weeks. Results: The study evaluated 35 patients (65.7% women), 19 allocated to the IG and 16 to the CG. The mean age was 55.5 ± 7.4 years. Most participants had completed the Brazilian middle school (up to the 8th grade; n = 28; 80.0%), had a family income of up to US$ 600 (n = 17; 48.6%) and practiced regular physical activity (n = 19; 54.3%). Two patients (5.7%) were smokers and 40.0% consumed alcohol regularly (n = 14). The IG showed a significant reduction in both SBP and DBP on the casual measurements and HBPM (p < 0.05) and in sodium excretion (p = 0.016). The CG showed a significant reduction only in casual SBP (p = 0.032). Conclusions: The light salt substitution for regular salt significantly reduced BP of hypertensive patients.

Carbon Stocks in Compartments of Soil Organic Matter 31 Years after Substitution of Native Cerrado Vegetation by Agroecosystems

ABSTRACT Changes in carbon stocks in different compartments of soil organic matter of a clayey Latossolo Vermelho Distrófico (Typic Haplustox), caused by the substitution of native savanna vegetation (cerrado sensu stricto) by agroecosystems, were assessed after 31 years of cultivation. Under native vegetation, a stock of 164.5 Mg ha-1 C was estimated in the 0.00-1.00 m layer. After 31 years of cultivation, these changes in soil C stocks were detected to a depth of 0.60 m. In the case of substitution of cerrado sensu stricto by no-tillage soybean-corn rotation, a reduction of at least 11 % of the soil C pools was observed. However, the adoption of no-tillage as an alternative to tillage with a moldboard plow (conventional system) reduced CO2 emissions by up to 12 %.

Annonaceae substitution rates: a codon model perspective

The Annonaceae includes cultivated species of economic interest and represents an important source of information for better understanding the evolution of tropical rainforests. In phylogenetic analyses of DNA sequence data that are used to address evolutionary questions, it is imperative to use appropriate statistical models. Annonaceae are cases in point: Two sister clades, the subfamilies Annonoideae and Malmeoideae, contain the majority of Annonaceae species diversity. The Annonoideae generally show a greater degree of sequence divergence compared to the Malmeoideae, resulting in stark differences in branch lengths in phylogenetic trees. Uncertainty in how to interpret and analyse these differences has led to inconsistent results when estimating the ages of clades in Annonaceae using molecular dating techniques. We ask whether these differences may be attributed to inappropriate modelling assumptions in the phylogenetic analyses. Specifically, we test for (clade-specific) differences in rates of non-synonymous and synonymous substitutions. A high ratio of nonsynonymous to synonymous substitutions may lead to similarity of DNA sequences due to convergence instead of common ancestry, and as a result confound phylogenetic analyses. We use a dataset of three chloroplast genes (rbcL, matK, ndhF) for 129 species representative of the family. We find that differences in branch lengths between major clades are not attributable to different rates of non-synonymous and synonymous substitutions. The differences in evolutionary rate between the major clades of Annonaceae pose a challenge for current molecular dating techniques that should be seen as a warning for the interpretation of such results in other organisms.

Reações de 1,2-dicloro-4,5-dinitrobenzeno com aminas: monossubstituição de nitro e dissubstituição de cloro e nitro

1,2-dichloro-4,5-dinitrobenzene (DCDNB) reacts with primary and secondary amines, in acetonitrile, at room temperature, to give a monosubstituted nitro product with a yield of 85 to 95%. The chloro-nitro-disubstituted product is formed with excess amine under reflux. Piperidine, pyrroline, dimethylamine and methylamine were the most reactive reagents in both mono- and disubstitution.

Biodiesel de soja: reação de transesterificação para aulas práticas de química orgânica

The transesterification procedure of triacylglycerides from soybean oil (in natura and waste oil) to give biodiesel was adapted to semi-micro laboratory scale as an additional experimental technique of nucleophilic acyl substitution for undergraduate courses in Chemistry and related areas.

Obtenção de biodiesel por transesterificação em dois estágios e sua caracterização por cromatografia gasosa: óleos e gorduras em laboratório de química orgânica

Methanolic transesterification of oils and fats was carried out in a two steps procedure, under basic and acidic catalysis. Palm, soybean, canola, corn, rice, grapeseed, sunflower, peanut, pequi and olive oils, besides tallow and lard were used as feedstock. Specific gravity, relative viscosity, thin layer chromatography and gas chromatography were used to characterize the biodiesel. Biodiesel was obtained in high yield and purity. Results were used to discuss the following key-concepts: 1 - triglycerides, composition and properties; 2 - nucleophilic acyl substitution under basic and acid conditions, 3 - thin layer chromatography, 4 - gas chromatography and its quantitative methods.

Impact of the substitution of reference annual streamflow by monthly streamflow on the potential use of water resources

The consideration of the streamflow seasonality has a high potential to improve the water use. In order to give subsidies to the optimization of water use, it was evaluated the impact of the change of reference annual streamflow by the monthly streamflows in the potential water use throughout the hydrography of Paracatu sub-Basin. It was evaluated the impact on Q7,10 (lowest average streamflow during a 7-day period with an average recurrence of 10 years) and on Q95 (permanent flow present 95% of the time). The use of monthly streamflow to substitute the annual streamflow had a high potential of improvement of water resources use in the sub-Basin studied. The use of monthly Q 7,10 in substitution of annual Q 7,10 increases the potential water use that vary from about 10% in the months of lower water availability to values exceeding 200% in the months with higher availability of surface water resources. The use of monthly Q95 in substitution of the annual Q95 implies in changes oscillating from reduction of 37% in months of higher water restriction to values exceeding 100% in the months of higher availability, so the use of monthly Q95 instead of the annual Q95 enables the more rational and safe use of water resources.

Substitution-Newton-Raphson method applied to the modeling of a vapour compression refrigeration system using different representations of the thermodynamic properties of R-134a

This paper gives a detailed presentation of the Substitution-Newton-Raphson method, suitable for large sparse non-linear systems. It combines the Successive Substitution method and the Newton-Raphson method in such way as to take the best advantages of both, keeping the convergence features of the Newton-Raphson with the low requirements of memory and time of the Successive Substitution schemes. The large system is solved employing few effective variables, using the greatest possible part of the model equations in substitution fashion to fix the remaining variables, but maintaining the convergence characteristics of the Newton-Raphson. The methodology is exemplified through a simple algebraic system, and applied to a simple thermodynamic, mechanical and heat transfer modeling of a single-stage vapor compression refrigeration system. Three distinct approaches for reproducing the thermodynamic properties of the refrigerant R-134a are compared: the linear interpolation from tabulated data, the use of polynomial fitted curves and the use of functions derived from the Helmholtz free energy.

Thr(118)Met amino acid substitution in the peripheral myelin protein 22 does not influence the clinical phenotype of Charcot-Marie-Tooth disease type 1A due to the 17p11.2-p12 duplication

The Thr(118)Met substitution in the peripheral myelin protein 22 (PMP22) gene has been detected in a number of families with demyelinating Charcot-Marie-Tooth (CMT1) neuropathy or with the hereditary neuropathy with liability to pressure palsy, but in none of them has it consistently segregated with the peripheral neuropathy. We describe here a CMT1 family (a 63-year-old man, his brother and his niece) in which two mutations on different chromosomes were found in the PMP22 gene, the 17p duplication, detected by fluorescent semiquantitative polymerase chain reaction (PCR) of microsatellite markers localized within the duplicated region on chromosome 17p11.2-p12, and the Thr(118)Met substitution, detected by direct sequencing the four coding exons of the PMP22 gene. A genotype/phenotype correlation study showed that the neuropathy segregates with the duplication and that the amino acid substitution does not seem to modify the clinical characteristics or the severity of the peripheral neuropathy. We did not find any evidence to characterize this substitution as a polymorphism in the population studied and we propose that the high frequency reported for this point mutation in the literature suggests that the Thr(118)Met substitution may be a hotspot for mutations in the PMP22 gene.

Partial substitution of nitrite by chitosan and the effect on the quality properties of pork sausages

The aim of the study was to evaluate the influence of partial nitrite replacement by chitosan on the quality of Ham Visking (a type of pork sausages). Five Ham Visking formulations were elaborated modifying the sodium nitrite (0.011; 0.016 or 0.0212%) and chitosan concentrations (0.25 or 0.5%) in the products. Sausages were stored at 4 ºC and physicochemical, microbiological, and sensorial evaluations were performed in order to estimate their shelf life. Chitosan can be used in pork sausages without affecting ensory attributes such as color although the panelists detected textural differences among the samples with chitosan, which suggests that there is some influence of deacetylation degree of chitosan on the textural behavior of sausages which still needed to be explained for a successful application of chitosan in meat products. The reduction of residual sodium nitrite did not affect the color and flavor of such products, but the use of chitosan increasedsignificantly the shelf life of sausages.

Industrialization in Sub-Saharan Africa and import substitution policy

This article aims to contribute to the understanding of the process of import substitution in Sub-Saharan Africa. The process of industrialization in Sub-Saharan Africa occurred in two phases: a first step, even very early during the colonial regime began around the 1920s and ended in the late forties; a second phase of industrialization began in the late fifties and gained momentum in the sixties, when import substitution was implemented more widely. Although these countries were the last to embark on the strategy of import substitution, they followed the same steps of Latin American countries, and as the structural domestic and external constraints were too strong, the failure of the policy of import substitution arrived early and the negative impact on these economies had a greater magnitude.

Identification of factors and groups at risk of infection with Schistosoma mansoni: a strategy for the implementation of control measures?

A fourteen year schistosomiasis control program in Peri-Peri (Capim Branco, MG) reduced prevalence from 43.5 to 4.4%; incidence from 19.0 to 2.9%, the geometric mean of the number of eggs from 281 to 87 and the level of the hepatoesplenic form cases from 5.9 to 0.0%. In 1991, three years after the interruption of the program, the prevalence had risen to 19.6%. The district consists of Barbosa (a rural area) and Peri-Peri itself (an urban area). In 1991, the prevalence in the two areas was 28.4% and 16.0% respectively. A multivariate analysis of risk factors for schistosomiasis indicated the domestic agricultural activity with population attributive risk (PAR) of 29.82%, the distance (< 10 m) from home to water source (PAR = 25.93%) and weekly fishing (PAR = 17.21%) as being responsible for infections in the rural area. The recommended control measures for this area are non-manual irrigation and removal of homes to more than ten meters from irrigation ditches. In the urban area, it was observed that swimming at weekly intervals (PAR = 20.71%), daily domestic agricultural activity (PAR = 4.07%) and the absence of drinking water in the home (PAR=4.29%) were responsible for infections. Thus, in the urban area the recommended control measures are the substitution of manual irrigation with an irrigation method that avoids contact with water, the creation of leisure options of the population and the provision of a domestic water supply. The authors call attention to the need for the efficacy of multivariate analysis of risk factors to be evaluated for schistosomiasis prior to its large scale use as a indicator of the control measures to be implemented.