Alterações estruturais in vivo dos isômeros todo-trans, 9-cis e 13-cis do beta-caroteno

Com o objetivo de verificar alterações estruturais nos isômeros todo-trans, 9- e 13-cis do beta-caroteno foi realizado um ensaio biológico baseado no modelo de esgotamento das reservas hepáticas de carotenóides em ratos. Animais depletados desses carotenóides receberam, durante quinze dias, os isômeros puros todo-trans, 9-cis e 13-cis do beta-caroteno. Ao final deste período, verificou-se a ocorrência de re-isomerização in vivo desses isômeros, a partir da quantificação dos mesmos depositados no fígado dos animais. Foi observada re-isomerização do 9-cis em todo-trans, do todo-trans em 9-cis, do 13-cis em 9-cis e todo-trans. O 13-cis foi mais susceptível à isomerização que o 9-cis, pois este último passou a todo-trans e nunca a 13-cis. Já o 13-cis, tanto pode se transformar em 9-cis quanto em todo-trans.

Isomerismo cis-trans: de Werner aos nossos dias

In coordination chemistry the study of geometrical isomerization and reactivity of specific isomers is a topic of major importance. The preparation of specific isomers often requires considerable complexity, and it is important to acquire a sense of what is involved in studying isomerism in laboratory. If it is difficult sometimes to prepare pure isomers, it is not easier to understand the mechanisms of isomerization reactions since studies on this subject have shown conflicting results and diferent interpretations on the same system have been reported in the literature. Although cis-trans isomerism in octahedral metal complexes is a common occurrence, there are relatively few studies reporting how these isomerizations occur. This paper gives an overview on cis-trans isomerization processes and identification of these species.

Incorporation of dietary trans monounsaturated fatty acids into tissues of Walker 256 tumor-bearing rats

The correlation between dietary trans fatty acids and neoplasia was examined in the present study. Walker 256 tumor-bearing and control rats were fed a trans monounsaturated fatty acid (MUFA)-rich diet for 8 weeks and the incorporation of trans fatty acids by tumor tissue was examined. Also, the effect of tumor growth on trans fatty acid composition of plasma and liver, and the content of thiobarbituric acid-reactive substances (TBARS) was determined. Walker 256 tumor cells presented both trans and cis MUFAs given in the diet. The equivalent diet proportions were 0.66 for trans and 1.14 for cis. Taking into consideration the proportion of trans MUFAs in plasma (11.47%), the tumor incorporated these fatty acids in a more efficient manner (18.27%) than the liver (9.34%). Therefore, the dietary trans fatty acids present in the diet are actively incorporated by the tumor. Tumor growth itself caused marked changes in the proportion of polyunsaturated fatty acids in the plasma and liver but provoked only slight modifications in both trans and cis MUFAs. Tumor growth also reduced the unsaturation index in both plasma and liver, from 97.79 to 86.83 and from 77.51 to 69.64, respectively. This effect was partially related to an increase in the occurrence of the lipid oxidation/peroxidation process of TBARS content which was increased in both plasma (from 0.428 to 0.505) and liver (from 9.425 to 127.792) due to tumor growth.

New insights into trypanosomatid U5 small nuclear ribonucleoproteins

Several protozoan parasites exist in the Trypanosomatidae family, including various agents of human diseases. Multiple lines of evidence suggest that important differences are present between the translational and mRNA processing (trans splicing) systems of trypanosomatids and other eukaryotes. In this context, certain small complexes of RNA and protein, which are named small nuclear ribonucleoproteins (U snRNPs), have an essential role in pre-mRNA processing, mainly during splicing. Even though they are well defined in mammals, snRNPs are still not well characterized in trypanosomatids. This study shows that a U5-15K protein is highly conserved among various trypanosomatid species. Tandem affinity pull-down assays revealed that this protein interacts with a novel U5-102K protein, which suggests the presence of a sub-complex that is potentially involved in the assembly of U4/U6-U5 tri-snRNPs. Functional analyses showed that U5-15K is essential for cell viability and is somehow involved with the trans and cis splicing machinery. Similar tandem affinity experiments with a trypanonosomatid U5-Cwc21 protein led to the purification of four U5 snRNP specific proteins and a Sm core, suggesting U5-Cwc-21 participation in the 35S U5 snRNP particle. Of these proteins, U5-200K was molecularly characterized. U5-200K has conserved domains, such as the DEAD/DEAH box helicase and Sec63 domains and displays a strong interaction with U5 snRNA.

A reatividade do estado excitado triplete de 1,3-indanodiona em benzeno

Rate constants for the quenching of 1,3-indandione (1) triplet by olefins and by hydrogen and electron donors were obtained employing the laser flash photolysis technique in benzene solution. These rate constants ranged from 2.5x10(5) Lmol-1s-1 (for 2-propanol) to 5.9x10(9) Lmol-1s-1 (for DABCO). From the quenching rate constants by 1,3-cyclohexadiene, trans- and cis-stilbene a value between 49.3 and 52.4 kcal/mol was estimated for the energy of the triplet state of 1,3-indandione. The npi* character of this triplet state was evidenced by the quenching rate constants obtained when typical hydrogen donors were employed as quenchers. For 2-phenyl-1,3-indandione (2, R=phenyl) a fast Norrish type I reaction is operating which prevents the determination of kinetic and spectroscopic data of its triplet state.

Sobre uma degenerescência acidental nos deslocamentos químicos de RMN de 31P{¹H} em complexos difosfínicos de rutênio

The [RuCl(bipy)(dppb)(4-pic)]PF6 complex was prepared and fully characterized. The X-ray crystal structure of this complex was determined in order to make an unambiguous distinction between the two possible positions of the 4-methylpyridine ligand (4-pic) in the compound: trans to phosphorus atom or trans to nitrogen atom. The [RuCl(bipy)(dppb)(4-pic)]PF6 complex exhibits an unusual temperature-dependent accidental degeneracy of the 31P chemical shifts in its solution NMR spectrum.

Determinação de resveratrol em sucos de uva no Brasil

A detecção de resveratrol em vinhos vem sendo estudada mais intensamente nos últimos anos. O isômero trans-resveratrol tem reconhecidas atividades biológicas, e algumas delas são de uso terapêutico, tais como ação antiinflamatória, inibição da enzima lipoxigenase e ação anticarcinogênica in vitro. A presença do composto resveratrol (4,3',5'-trihidroxiestilbeno), em seus isômeros (trans e cis), foi determinada nos diferentes tipos de sucos de uva produzidos no Brasil. Além destes, também foram quantificados os polifenóis totais, acidez, açúcares redutores, sólidos solúveis e densidade, em conformidade com a legislação vigente. O resveratrol foi quantificado por cromatografia líquida de alta eficiência segundo SOUTO et al. [23], com adaptação da temperatura para 50° C. Foi detectada a presença de trans-resveratrol em todos os sucos analisados na concentração de 0,19mg.L-1 a 0,90mg.L-1 e o isômero cis-resveratrol foi de 0,07 a 1,59mg.L-1 .

Exploración estocástica de las superficies de energía potencial de dímeros cis-trans y trans-trans del ácido fórmico

Potential energy surface (PES) of cis-trans and trans-trans formic acid dimers were sampled using a stochastic method, and the geometries, energies, and vibrational frequencies were computed at B3LYP/6-311++G(3df,2p) level of theory. The results show that molar free energy of dimerization deviated up to 108.4% when basis set superposition error (BSSE) and zero-point energy (ZPE) were not considered. For cis-trans dimers, C=O and O - H bond weakened, whereas C - O bonds strengthened due to dimerization. Also, trans-trans FA dimers did not show a trend regarding strengthening or weakening of the C=O, O - H and C - O bonds.

Pre-mRNA trans-splicing: from kinetoplastids to mammals, an easy language for life diversity

Since the discovery that genes are split into intron and exons, the studies of the mechanisms involved in splicing pointed to presence of consensus signals in an attempt to generalize the process for all living cells. However, as discussed in the present review, splicing is a theme full of variations. The trans-splicing of pre-mRNAs, the joining of exons from distinct transcripts, is one of these variations with broad distribution in the phylogenetic tree. The biological meaning of this phenomenon is discussed encompassing reactions resembling a possible noise to mechanisms of gene expression regulation. All of them however, can contribute to the generation of life diversity.

Footprints of a trypanosomatid RNA world: pre-small subunit rRNA processing by spliced leader addition trans-splicing

The addition of a capped mini-exon [spliced leader (SL)] through trans-splicing is essential for the maturation of RNA polymerase (pol) II-transcribed polycistronic pre-mRNAs in all members of the Trypanosomatidae family. This process is an inter-molecular splicing reaction that follows the same basic rules of cis-splicing reactions. In this study, we demonstrated that mini-exons were added to precursor ribosomal RNA (pre-rRNA) are transcribed by RNA pol I, including the 5' external transcribed spacer (ETS) region. Additionally, we detected the SL-5'ETS molecule using three distinct methods and located the acceptor site between two known 5'ETS rRNA processing sites (A' and A1) in four different trypanosomatids. Moreover, we detected a polyadenylated 5'ETS upstream of the trans-splicing acceptor site, which also occurs in pre-mRNA trans-splicing. After treatment with an indirect trans-splicing inhibitor (sinefungin), we observed SL-5'ETS decay. However, treatment with 5-fluorouracil (a precursor of RNA synthesis that inhibits the degradation of pre-rRNA) led to the accumulation of SL-5'ETS, suggesting that the molecule may play a role in rRNA degradation. The detection of trans-splicing in these molecules may indicate broad RNA-joining properties, regardless of the polymerase used for transcription.

Optimization of a HPLC procedure for simultaneous determination of cisplatin and the complex cis,cis,trans-diamminedichlorodihydroxoplatinum(IV) in aqueous solutions

A RP-HPLC procedure for the simultaneous determination of cisplatin and the complex cis,cis,trans-diamminedichlorodihydroxo-platinum(IV), was development. The developed procedure was validated in terms of linearity, accuracy, precision, limits of detection (LOD), limits of quantification (LOQ) and specificity. The limits of detection (LOD) were 0.47 x 10-4 and 0.53 x 10-4 mol L-1 and the limits of quantification (LOQ) were 1.57 x 10-4 and 1.75 x 10-4 mol L-1, for cisplatin and cis,cis,trans-diamminedichlorodihydroxopla-tinum(IV), respectively. The average recoveries of cisplatin and cis,cis,trans-diamminedichlorodihydroxoplatinum(IV) was 100.6% ± 1.4 and 101.2% ± 1.1, respectively. Intermediate (inter-day) precision, repeatability and specificity of the procedure for hydrolysis products of cisplatin were studied. The results of the study showed that the proposed RP-HPLC procedure is simple, rapid, precise, accurate and specific.

Cardiovascular responses to microinjection of trans-(±)-ACPD into the NTS were similar in conscious and chloralose-anesthetized rats

The changes in mean arterial pressure (MAP) and heart rate (HR) in response to the activation of metabotropic receptors in the nucleus tractus solitarii (NTS) with trans-(±)-1-amino-1,3-cyclopentanedicarboxylic acid (trans-(±)-ACPD) were evaluated in conscious and anesthetized Wistar, male rats weighing 240-260 g (N = 8). The responses obtained with trans-(±)-ACPD were compared with the responses to L-glutamate (1 nmol/100 nl), since in a previous study we showed that anesthesia converted a pressor response to L-glutamate microinjected into the NTS of conscious rats to a depressor response in the same rats under urethane or chloralose anesthesia. Microinjection of 3 doses of trans-(±)-ACPD (100, 500 and 1000 pmol/100 nl) produced a dose-dependent fall in MAP (range, -20 to -50 mmHg) and HR (range, -30 to -170 bpm) under both conscious and chloralose anesthesia conditions. These data indicate that the cardiovascular responses to the activation of metabotropic receptors by trans-(±)-ACPD are not affected by chloralose anesthesia while the cardiovascular responses to the activation of excitatory amino acid (EAA) receptors by L-glutamate are significantly altered

Trans-sialidase delivered as a naked DNA vaccine elicits an immunological response similar to a Trypanosoma cruzi infection

Trypanosoma cruzi, the protozoan parasite that causes Chagas' disease, does not synthesize sialic acid, but expresses a trans-sialidase (TS) that catalyzes the transfer of sialic acid from host glycoconjugates to the parasite surface. Here, we review studies that characterize the immune response to the catalytic domain of the enzyme in humans during Chagas' disease or in mice following immunization with the TS gene. In both cases, there are antibodies that strongly inhibit the enzymatic activity and generation of interferon-g-producing T cells.

Trans fatty acid intake among the population of the city of São Paulo, Brazil

OBJECTIVE: To analyze the monounsaturated and polyunsaturated trans fatty acid intake among the general population. METHODS: A cross-sectional study was conducted in São Paulo, Southeastern Brazil, in 2003, on a representative sample of 2,298 male and female subjects, including 803 adolescents (12 to 19 years), 713 adults (20 to 59 years) and 782 elderly people (60 years or over). Food intake was measured using 24-hour recall. Mean trans fatty acid intake was described according to gender and age group. RESULTS: The mean trans fatty acid intake was 5.0 g/day (SE = 0.1), accounting for 2.4% (SE = 0.1) of total energy and 6.8% (SE = 0.1) of total lipids. The adolescents had the highest mean intake levels (7.4 g/day; 2.9% of energy) while the adults and the elderly had similar intake (2.2% of energy for both; 6.4% of lipids and 6.5% of lipids, respectively). The mean trans fatty acid intake among adult and elderly women (approximately 2.5% of energy and 7.0% of lipids) was higher than among men in the same age group. The food item with the highest contribution towards trans fatty acids was margarine, accounting for more than 30% of total intake, followed by filled cookies among adolescents and meat among adults and the elderly. CONCLUSIONS: The trans fatty acid intake is above the level recommended by the World Health Organization. Replacement of the trans fatty acids in manufactured food items may be an effective measure for reducing trans fatty acid intake in Brazil.

ELEVATED TRANS-MAMMARY TRANSMISSION OF Toxocara canis LARVAE IN BALB/c MICE

Toxocariasis is a widespread zoonosis and is considered an important worldwide public health problem. The aim of this study was to investigate the frequency of trans-mammary Toxocara canis infection in newborn BALB/c mice nursed by females experimentally infected with 1,200 eggs after delivery. After 50 days of age, the presence of larvae in different organs of the offspring was investigated. Trans-mammary infection was confirmed in 73.9% of the mice that had been nursed by infected females. These data show a high trans-mammary transmission of T. canis and confirm the significance of this transmission route in paratenic hosts.