The present study evaluated the effects of heat stress on the ram seminal plasma proteome. Six Morada Nova rams were scrotal insulated for 8 days. Scrotal circumference, sperm parameters, and seminal fluid proteins were evaluated before (Day 0) and twice during scrotal insulation (Days 4 and 8), and weekly until semen parameters returned to preinsulation values (normal). Seminal proteins were analyzed by two-dimensional SDS-PAGE and mass spectrometry. Scrotal circumference decreased from 30 ± 0.4 cm on Day 0 to 22.6 ± 0.6 cm on Day 36 (P < 0.05) and became equivalent to preinsulation values on Day 71. Motile sperm became nearly absent from Day 8 to Day 64 but returned to normal on Day 113. Percentage of normal sperm changed similarly and returned to normal on Day 106. Rams were azoospermic between Days 29 and 64, and sperm concentration came back to normal on Day 92. The number of spots/two-dimensional gel reduced from 256 ± 31 on Day 0 to 104 ± 14 on Day 29 (when rams were azoospermic) and then increased to 183 ± 9 on Day 113 (P < 0.05), similar to spot counts before insulation. The intensities of 24 spots, referring to 17 seminal plasma proteins, were affected by treatment (P < 0.05). After insulation, seminal plasma had greater expression of actin (two isoforms), albumin, heat shock protein 70 kDa, protein DJ-1, HRPE773-like, C-reactive protein precursor, bodhesin-2 (one isoform), spermadhesins. Most protein spots had the greatest intensity between Days 8 and 29, returning to preinsulation values on Day 113 (when many sperm criteria returned to normal). Proteins downregulated after scrotal insulation included dipeptidyl peptidase 3, isoforms of heat shock protein 90 kDa, RSVP22, MMP2 and of Bdh2. In this case, RSVP22 was reduced on Day 113 and all others, on Day 134. Expression of MMP2 and HSP90.1 was reduced throughout the study. Integrin β5, V-type H(+)-ATPase subunit A, ZBTB 42-like protein, isoforms of Bdh2, PSP-I, and RSVP22 were upregulated after testis insulation. Intensities of these spots were maximum (P < 0.05) 8 days after insulation started or on Day 29. Expression of most of such proteins returned to normal on Day 113. In conclusion, scrotal insulation affected testis and sperm parameters of rams, indicating alterations in both spermatogenesis and sperm maturation. Changes of seminal plasma proteome were coincidental with variations in semen parameters. Proteins affected by heat challenge are potentially involved in sperm protection, maturation, and fertilization.

In this article a mild, simple, safe, and chemoselective synthesis and reduction of o-quinone methides to the corresponding 3-alkyl-2-hydroxy-1,4-naphthoquinones, compounds with interesting biological activity, mediated by the formic acid-water system is described. This new one-pot methodology was applied to the synthesis of lapachol and constitutes an efficient and inexpensive alternative for the preparation of this natural bioactive compound

No abstract

BackgroundThe hydroxynaphthoquinones have been extensively investigated over the past 50 years for their anti-malarial activity. One member of this class, atovaquone, is combined with proguanil in Malarone®, an important drug for the treatment and prevention of malaria.MethodsAnti-malarial activity was assessed in vitro for a series of 3-alkyl-2-hydroxy-1,4-naphthoquinones (N1-N5) evaluating the parasitaemia after 48 hours of incubation. Potential cytotoxicity in HEK293T cells was assessed using the MTT assay. Changes in mitochondrial membrane potential of Plasmodium were measured using the fluorescent dye Mitrotracker Red CMXROS.ResultsFour compounds demonstrated IC50s in the mid-micromolar range, and the most active compound, N3, had an IC50 of 443 nM. N3 disrupted mitochondrial membrane potential, and after 1 hour presented an IC50ΔΨmit of 16 μM. In an in vitro cytotoxicity assay using HEK 293T cells N3 demonstrated no cytotoxicity at concentrations up to 16 μM.ConclusionsN3 was a potent inhibitor of mitochondrial electron transport, had nanomolar activity against cultured Plasmodium falciparum and showed minimal cytotoxicity. N3 may serve as a starting point for the design of new hydroxynaphthoquinone anti-malarials.

Recebido em 15/1/09; aceito em 20/3/09; publicado na web em 2/4/09POTeNTIAlITy AND OPPORTUNITy IN The CheMISTRy OF SUCROSe AND OTheR SUGARS. Non-renewable biomass, such as coal, oil and natural gas are not only energy sources but also important starting materials for the production of a variety of chemicals ranging from gasoline, diesel oil and fine chemicals. In this regard, carbohydrates, the most abundant class of enantiopure organic compounds, are very suitable for generation of chemicals of great practical value. Their bulk-scale availability associated with low cost make them unique starting materials for organic preparative purpose. They are a most attractive alternative for construction of enantiopure target molecules by asymmetric synthesis. This review addresses, in addition to the use of low molecular weight carbohydrates, issues related to renewable biomass from photosynthesis and alternatives for the production of bulk and fine chemicals.Keywords: renewable biomass; sucrose; carbohydrates. introduçÃoA biomassa renovável terrestre é constituída de diversos produtos de baixas e altas massas moleculares como, por exemplo, carboidratos, aminoácidos, lipídios, e biopolímeros, como celulose, hemicelulose, quitina, amido, lignina e proteínas. estas biomassas são utilizadas na alimentação e para a produção de uma variedade de combustíveis, produtos químicos e produtos energéticos. O processamento da biomassa renovável abrange métodos biológicos, térmicos e/ou transformações químicas, além de tratamento mecânico para obter combustíveis sólidos, líquidos ou gasosos ou ainda produtos químicos de maior valor agregado.As biomassas não-renováveis, como carvão, petróleo e gás natural não são apenas materiais energéticos naturais, mas também são importantes insumos para a produção de uma grande variedade de produtos químicos que variam desde gasolina e óleo diesel 1-3 a insumos químicos e intermediários de produtos da química fina. 4,5 em termos energéticos, estas três biomassas são responsáveis por aproximadamente 75% da energia consumida correspondendo a 33, 24 e 19%, respectivamente.6 No entanto, como são recursos naturais fósseis finitos, fica evidente a grande necessidade de se desenvolver tecnologia para o aproveitamento das biomassas renováveis (esquema 1).As biomassas oriundas de fontes renováveis e o carvão foram as matérias-primas utilizadas, na mesma proporção, pela humanidade até cerca de 100 anos atrás. A partir do início do século 20 o gás natural e o petróleo tornaram-se os principais componentes da matriz energética mundial, alcançando seu ápice no século 21, o que reduziu drasticamente o uso das biomassas renováveis e paralelamente foram crescendo os níveis de CO 2 na atmosfera, devido à queima de gás e petróleo associado às devastações nas florestas.O petróleo tornou-se a biomassa de origem fóssil mais importante e as previsões de que sua produção não seria reduzida antes de 2050 fizeram com que as indústrias químicas continuassem baseando seus processos nesta matéria-prima. Como consequência, uma...

The preparation of 1H-1,2,3-, 2H-1,2,3-, 1H-1,2,4- and 4H-1,2,4-triazole derivatives brings to light several issues. There is a need to find new, more efficient preparations for these triazoles that take into consideration current issues in green chemistry, energy saving and sustainability. New diseases are discovered and new viruses and bacteria continue to challenge mankind, so it is imperative to find new prototypes for these new diseases. Of great urgency is finding prototypes against bacteria that continue to increase resistance and for neglected diseases that affect a large part of humanity, especially the poor and vulnerable.

No abstract

A synthetic method to obtain α- and β-pyran naphthoquinones 10 and 11 with a hydroxyl substituent on the aromatic ring was developed. Two series of α- and β-pyran naphthoquinones were obtained from the 8-hydroxy-lawsone, and their anticancer properties were evaluated against four tumor cell lines. In general, the new compounds displayed good activity, possibly indicating that these compounds have increased pro-oxidant capacity. The 9-hydroxy-α-lapachone and 7-hydroxy-β-lapachone analogues of the natural products α-lapachone and β-lapachone were successfully produced by this methodology.