Chemical profile of rums as a function of their origin. The use of chemometric techniques for their identification

To identify chemical descriptors to distinguish Cuban from non-Cuban rums, analyses of 44 samples of rum from 15 different countries are described. To provide the chemical descriptors, analyses of the the mineral fraction, phenolic compounds, caramel, alcohols, acetic acid, ethyl acetate, ketones, and aldehydes were carried out. The analytical data were treated through the following chemometric methods: principal component analysis (PCA), partial least square-discriminate analysis (PLS-DA), and linear discriminate analysis (LDA). These analyses indicated 23 analytes as relevant chemical descriptors for the separation of rums into two distinct groups. The possibility of clustering the rum samples investigated through PCA analysis led to an accumulative percentage of 70.4% in the first three principal components, and isoamyl alcohol, n-propyl alcohol, copper, iron, 2-furfuraldehyde (furfuraldehyde), phenylmethanal (benzaldehyde), epicatechin, and vanillin were used as chemical descriptors. By applying the PLS-DA technique to the whole set of analytical data, the following analytes have been selected as descriptors: acetone, sec-butyl alcohol, isobutyl alcohol, ethyl acetate, methanol, isoamyl alcohol, magnesium, sodium, lead, iron, manganese, copper, zinc, 4-hydroxy3,5-dimethoxybenzaldehyde (syringaldehyde), methaldehyde (formaldehyde), 5-hydroxymethyl-2furfuraldehyde (5-HMF), acetalclehyde, 2-furfuraldehyde, 2-butenal (crotonaldehyde), n-pentanal (valeraldehyde), iso-pentanal (isovaleraldehyde), benzaldehyde, 2,3-butanodione monoxime, acetylacetone, epicatechin, and vanillin. By applying the LIDA technique, a model was developed, and the following analytes were selected as descriptors: ethyl acetate, sec-butyl alcohol, n-propyl alcohol, n-butyl alcohol, isoamyl alcohol, isobutyl alcohol, caramel, catechin, vanillin, epicatechin, manganese, acetalclehyde, 4-hydroxy-3-methoxybenzoic acid, 2-butenal, 4-hydroxy-3,5-dimethoxybenzoic acid, cyclopentanone, acetone, lead, zinc, calcium, barium, strontium, and sodium. This model allowed the discrimination of Cuban rums from the others with 88.2% accuracy.

Multivariate analysis for the classification and differentiation of Madeira wines according to main grape varieties

In order to differentiate and characterize Madeira wines according to main grape varieties, the volatile composition (higher alcohols, fatty acids, ethyl esters and carbonyl compounds) was determined for 36 monovarietal Madeira wine samples elaborated from Boal, Malvazia, Sercial and Verdelho white grape varieties. The study was carried out by headspace solid-phase microextraction technique (HS-SPME), in dynamic mode, coupled with gas chromatography–mass spectrometry (GC–MS). Corrected peak area data for 42 analytes from the above mentioned chemical groups was used for statistical purposes. Principal component analysis (PCA) was applied in order to determine the main sources of variability present in the data sets and to establish the relation between samples (objects) and volatile compounds (variables). The data obtained by GC–MS shows that the most important contributions to the differentiation of Boal wines are benzyl alcohol and (E)-hex-3-en-1-ol. Ethyl octadecanoate, (Z)-hex-3-en-1-ol and benzoic acid are the major contributions in Malvazia wines and 2-methylpropan-1-ol is associated to Sercial wines. Verdelho wines are most correlated with 5-(ethoxymethyl)-furfural, nonanone and cis-9-ethyldecenoate. A 96.4% of prediction ability was obtained by the application of stepwise linear discriminant analysis (SLDA) using the 19 variables that maximise the variance of the initial data set.

Physico-chemical and harvest time alterations in pineapple fruits Smooth Cayenne caused by paclobutrazol

O objetivo deste trabalho foi avaliar o efeito de um inibidor da diferenciação floral nas características físico-químicas dos frutos do abacaxizeiro, bem como, no período de colheita. Utilizou-se paclobutrazol a 100, 150 e 200 mg L-1 aplicados 2, 3 ou 4 vezes, em plantas de abacaxi cv. Smooth Cayenne. Os tratamentos não influenciaram nas características químicas dos frutos, e mesmo alterando algumas características físicas, os frutos permaneceram dentro dos padrões de qualidade para comercialização. O período de colheita foi ampliado em todos os tratamentos comparando-se com o controle, porém, 150 mg L-1 aplicados 2 vezes promoveu melhor resultado analisando-se em conjunto a época de colheita com a massa fresca do fruto.

Optical chemical sensors using polythiophene derivatives as active layer for detection of volatile organic compounds

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Endocrine Disruptors and Hypothalamic Sexual Differentiation

The so-called endocrine disruptors have been described as compounds which interfere with the estrogen action in their receptors and may exert a crucial role in the development of the reproductive tract and in the brain sexual differentiation. Thus, conducts and/or exposure to these drugs in the perinatal period that apparently do not endanger the neonate may cause side effects. During embrionary development, the gonads, through discharge of a small quantity of reproductive hormones, will guarantee the phenotype of male or female at birth, as well as actuate in specific areas sexual differentiation of the central nervous system. Several experimental models have shown an interference of drugs acting as endocrine disruptors in hypothalamic sexual differentiation. Thus, reproductive function is impaired by exposure to estrogen in the perinatal life of rats and the mechanisms involved in this effect are distinct for males and females. Perinatal exposure to drugs which may be considered endocrine disrupters may induce an incomplete masculinization and defeminization of the central nervous system. Alterations in these processes, if present, generally are perceived only at puberty or adult reproductive life. These later alterations may include anomalies in the process of fertility or in sexual behavior.

Effects of abiotic factors on growth and chemical defenses in cultivated clones of Laurencia dendroidea J. Agardh (Ceramiales, Rhodophyta)

Laurencia dendroidea shows high inter- and intrapopulation variability in the amount of the sesquiterpene elatol, caused by genetic variation as well as environmental factors. To test the independent effect of physical and nutritional conditions, the growth and the levels of elatol in L. dendroidea clones were evaluated under different conditions of temperature, salinity, irradiance, and culture medium in the laboratory. Growth of L. dendroidea was clearly affected by all these factors, but elatol levels were influenced only by temperature and salinity. Better conditions for growth did not produce a similar effect on elatol production in L. dendroidea, contradicting the carbon/nutrient balance and growth/differentiation balance models. On the contrary, severe conditions of temperature and salinity promoted a decrease in elatol levels, as predicted by the environmental stress model. Our results using clones indicated that abiotic factors clearly take part in fostering chemical variations observed in natural populations, in addition to genetic factors, and can promote differential susceptibility of plant specimens to natural enemies.

Optical chemical sensors using polythiophene derivatives as active layer for detection of volatile organic compounds

Several studies on polythiophene gas sensors, based mainly on electrochemical and gravimetric principles can be found in the literature. However, other principles of gas detection, such as optical and thermal, are still little studied. Optical sensing is suitable for remote detection and offers great versatility at low cost. Here,we report on the use of thin films of seven polythiophene derivatives as active layer in optical sensors for the detection of six volatile organic compounds (n-hexane, toluene, tetrahydrofuran, chloroform, dichloromethane and methanol) and water vapor, in concentration range of 500-30,000 ppm. The results showed that it is possible to use different polythiophene derivatives to differentiate VOCs by optical sensing. Differentiation can be performed based on the presence or not of response to an analyte and the sensitivity value of the sensors for the analytes. Another important feature is the lack of the effect of humidity on the response of most films, which could be a major drawback in the application of these sensors. (C) 2011 Elsevier B.V. All rights reserved.

Mesenchymal Stromal Cells (MSCs) and induced Plutipotent Stem Cells (iPSCs) in Domestic Animals: Characterization and Differentiation Potential

Derivation of stem cell lines from domesticated animals has been of great interest as it benefits translational medicine, clinical applications to improve human and animal health and biotechnology. The main types of stem cells studied are Embryonic Stem Cells (ESCs), induced Pluripotent Stem Cells (iPSCs) and Mesenchymal Stem/Stromal Cells (MSCs). This thesis had two main aims: (I) The isolation of bovine MSCs from amniotic fluid (AF) at different trimesters of pregnancy and their characterization to study pluripotency markers expression. Stemness markers were studied also in MSCs isolated from equine AF, Wharton’s jelly (WJ) and umbilical cord blood (UCB) as continuation of the characterization of these cells previously performed by our research group; (II) The establishment and characterization of iPSCs lines in two attractive large animal models for biomedical and biotechnology research such as the bovine and the swine, and the differentiation into the myogenic lineage of porcine iPSCs. It was observed that foetal tissues in domestic animals such as the bovine and the horse represent a source of MSCs able to differentiate into the mesodermal lineage but they do not proliferate indefinitely and they lack the expression of many pluripotency markers, making them an interesting source of cells for regenerative medicine, but not the best candidate to elucidate pluripotency networks. The protocol used to induce pluripotency in bovine fibroblasts did not work, as well as the chemical induction of pluripotency in porcine fibroblasts, while the reprogramming protocol used for porcine iPSCs was successful and the line generated was amenable to being differentiated into the myogenic lineage, demonstrating that they could be addressed into a desired lineage by genetic modification and appropriated culture conditions. Only a few cell types have been differentiated from domestic animal iPSCs to date, so the development of a reliable directed-differentiation protocol represents a very important result.

Core formation and mantle differentiation on Mars

Geochemical investigation of Martian meteorites (SNC meteorites) yields important constraints on the chemical and geodynamical evolution of Mars. These samples may not be representative of the whole of Mars; however, they provide constraints on the early differentiation processes on Mars. The bulk composition of Martian samples implies the presence of a metallic core that formed concurrently as the planet accreted. The strong depletion of highly siderophile elements in the Martian mantle is only possible if Mars had a large scale magma ocean early in its history allowing efficient separation of a metallic melt from molten silicate. The solidification of the magma ocean created chemical heterogeneities whose ancient origin is manifested in the heterogeneous 142Nd and 182W abundances observed in different meteorite groups derived from Mars. The isotope anomalies measured in SNC meteorites imply major chemical fractionation within the Martian mantle during the life time of the short-lived isotopes 146Sm and 182Hf. The Hf-W data are consistent with very rapid accretion of Mars within a few million years or, alternatively, a more protracted accretion history involving several large impacts and incomplete metal-silicate equilibration during core formation. In contrast to Earth early-formed chemical heterogeneities are still preserved on Mars, albeit slightly modified by mixing processes. The preservation of such ancient chemical differences is only possible if Mars did not undergo efficient whole mantle convection or vigorous plate tectonic style processes after the first few tens of millions of years of its history.

Function of GCIP (CCNDBP1), a helix -loop -helix leucine -zip protein, in cell differentiation and tumorigenesis

Cell growth and differentiation are complex and well-organized processes in which cells respond to stimuli from the environment by carrying out genetic programs. Transcription factors with helix-loop-helix (HLH) motif play critical roles in controlling the expression of genes involved in lineage commitment, cell fate determination, proliferation and tumorigenesis. This study has examined the roles of GCIP (CCNDBP1) in cell differentiation and tumorigenesis. GCIP is a recently identified HLH-leucine zipper protein without a basic region like the Id family of proteins. However, GCIP shares little sequence homology with the Id proteins and has domains with high acidic amino acids and leucine-rich regions following the HLH domain like c-Myc. Here we firstly demonstrate that GCIP is a transcription regulator related to muscle differentiation program. Overexpression of GCIP in C2C12 cells not only promotes myotube formation but also upregulates myogenic differentiation biomarkers, including MHC and myogenein. On the other hand, our finding also suggests that GCIP is a potential tumor suppressor related to cell cycle control. Expression of GCIP was significantly down-regulated in colon tumors as compared to normal colon tissues. Overexpression of GCIP in SW480 colon cancer cell line resulted in a significant inhibition on tumor cell colony formation on soft agar assays while silencing of GCIP expression by siRNA can promote cell proliferation and colony formation. In addition, results from transgenic mice specifically expressing GCIP in liver also support the idea that GCIP is involved in the early stage of hepatocarcinogenesis and decreased susceptibility to chemical hepatocarcinogenesis. ^

(Table 3) Chemical analyses from DSDP Holes 22-214, 22-215 and 22-216 in the Indian Ocean

The basalts and oceanic andesites from the aseismic Ninetyeast Ridge display trachytic, vesicular and amygdaloidal textures suggesting a subaerial volcanic environment. The normative composition of the Ninetyeast Ridge ranges from olivine picriteto nepheline-normative alkaline basalt, suggesting a wide range of differentiation. This is further supported by the fractionation-differentiation trends displayed by transition metal trace elements (Ni, Cr, V and Cu). The Ninetyeast Ridge rocks are enriched in rare earth (RE) and large ion lithophile (LIL) elements and Sr isotopes (0.7043-0.7049), similar to alkali basalts and tholeiites from seamounts and islands, but different from LIL-element-depleted tholeiitic volcanic rocks of the recent seismic mid-Indian oceanic ridge. The constancy of 87Sr/86Sr ratios for basalts and andesites is compatible with a model involving fractional crystallization of mafic magma. The variation of 87Sr/86Sr ratios between 0.97 and 2.79 may possibly be explained in terms of a primordial hot mantle and/or chemically contrasting heterogeneous mantle source layers relatively undepleted in LIL elements at different periods in the geologic past. In general, the Sr isotopic data for rocks from different tectonic environments are consistent with a "zoning-depletion model" with systematically arranged alternate alkali-poor and alkali-rich layers in the mantle beneath the Indian Ocean.

Chemical composition of basalts and minerals from basalts of the Bouvet triple junction

This study focuses on mafic volcanic rocks from the Bouvet triple junction, which fall into six geochemically distinct groups: (1) N-MORB, the most widespread type, encountered throughout the study area. (2) Subalkaline volcanics, hawaiites and mugearites strongly enriched in lithophile elements and radiogenic isotopes and composing the Bouvet volcanic rise, and compositionally similar basalts and basaltic andesites from the Spiess Ridge, generated in a deeper, fertile mantle region. (3) Relatively weakly enriched basalts, T-MORB derived by the mixing of Type 1 and 2 melts and exposed near the axes of the Mid-Atlantic, Southwest Indian, and America-Antarctic Ridges. (4) Basalts with a degree of trace lithophile element enrichment similar to the Spiess Ridge and Bouvet Island rocks, but higher in K, P, Ti, and Cr. These occur within extensional structures: the rift valley of the Southwest Indian Ridge, grabens of the East Dislocation Zone, and the linear rise between the Spiess Ridge and Bouvet volcano. Their parental melts presumably separated from plume material that spread from the main channels and underwent fluid-involving differentiation in the mantle. (5) A volcanic suite ranging from basalt to rhyolite, characterized by low concentrations of lithophile elements, particularly TiO2, and occurring on the Shona Seamount and other compressional features within the Antarctic and South American plates near the Bouvet triple junction. Unlike Types 1 to 4, which display tholeiitic differentiation trends, this suite is calc-alkaline. Its parental melts were presumably related to the plume material as well but, subsequently, they underwent a profound differentiation involving fluids and assimilated surrounding rocks in closed magma chambers in the upper mantle. Alternatively, the Shona Seamount might be a fragment of an ancient oceanic island arc. (6) Enriched basalts, distinguished from the other enriched rock types in very high P and radiogenic isotope abundances and composing a tectonic uplift near the junction of the three rifts. It thus follows that the main factors responsible for the compositional diversity of volcanic rocks in this region include (i) mantle source heterogeneity, (ii) plume activity, (iii) an intricate geodynamic setup at the triple junction giving rise to stresses in adjacent plate areas, and (iv) the geological prehistory. The slow spreading rate and ensuing inefficient mixing of the heterogeneous mantle material result in strong spatial variations in basaltic compositions.

Chemical composition of basalts and basaltic glasses from the Sierra Leone Fracture Zone region

Major and trace element (including REE) geochemistry of basalts and chilled basaltic glasses from the MAR axial zone in the vicinity of the Sierra Leone FZ (5-7°10'N) has been studied. Associations of basalts of various compositions with particular ocean-floor geological structural features have been analyzed as well. Three basaltic varieties have been discriminated. Almost ubiquitous are high-Mg basalts (Variety 1) that are derivatives of N-MORB tholeiitic melts and that are produced in the axial zone of spreading. Variety 2 is alkaline basalts widespread on the southwestern flank of the MAR crest zone in the Sierra Leone region, likely generated through deep mantle melting under plume impact. Variety 3 is basalts derivative from T- and P-MORB-like tholeiitic melts and originating through addition of deeper mantle material to depleted upper mantle melts. Magma generation parameters, as calculated from chilled glass compositions, are different for depleted tholeiites (44-55 km, 1320-1370°C) and enriched tholeiites (45-78 km, 1330-1450°C). Mantle plume impact is shown to affect not only tholeiitic basalt compositions but also magma generation conditions in the axial spreading zone, resulting in higher Ti and Na concentrations in melts parental to rift-related basalts occurring near the plume. T- and P-MORBs are also developed near areas where mantle plumes are localized. High-Mg basalts are shown to come in several types with distinctive Ti and Na contents. Nearly every single MAR segment (bounded by sinistral strike slips and the Bogdanov Fracture Zone) is featured by its own basalt type suggesting that it has formed above an asthenospheric diapir with its unique magma generation conditions. These conditions are time variable. Likely causes of temporal and spatial instability of the mantle upwelling beneath this portion of the MAR are singular tectonic processes and plume activity. In sulfide-bearing rift morphostructures (so-called "Ore area'' and the Markov Basin), basalts make up highly evolved suites generated through olivine and plagioclase fractionation, which is suggestive of relatively long-lived magma chambers beneath the sulfide-bearing rift morphostructures. Functioning of these chambers is a combined effect of singular geodynamic regime and plume activity. In these chambers melts undergo deep differentiation leading to progressively increasing concentration of sulfide phase, eventually to be supplied to the hydrothermal plumbing system.

Chemical composition of rocks and minerals from the Karymsky volcanic center, Eastern Kamchatka

The powerful eruption in the Akademii Nauk caldera on January 2, 1996 marked a new activity phase of the Karymsky volcano and became a noticeable event in the history of modern volcanism in Kamchatka. The paper reports data obtained by studying more than 200 glassy melt inclusions in phenocrysts of olivine (Fo82-72), plagioclase (An92-73), and clinopyroxene (Mg# 83-70) in basalts of the 1996 eruption. The data were used to estimate composition of the parental melt and physicochemical parameters of the magma evolution. According to our data, the parental melt corresponded to low magnesium, high aluminum basalt (SiO2 = 50.2%, MgO = 5.6%, Al2O3 = 17%) of the mildly potassium type (K2O = 0.56%) and contained much dissolved volatile components (H2O = 2.8%, S = 0.17%, and Cl = 0.11%). Melt inclusions in the minerals are similar in chemical composition, a fact testifying that the minerals crystallized simultaneously with one another. Their crystallization started at pressure ~1.5 kbar, proceeded within a narrow temperature range of 1040+/-20°C, and continued until near-surface pressure ~100 bar was reached. Degree of crystallization of the parental melt during its eruption was close to 55%. Massive crystallization was triggered by H2O degassing under pressure <1 kbar. Magma degassing in an open system resulted in escape of 82% H2O, 93% S, and 24% Cl (of their initial contents in the parental melt) to the fluid phase. Release of volatile compounds to the atmosphere during the eruption that lasted for 18 h was estimated as 1.7x10**6 t H2O, 1.4x10**5 t S, and 1.5x10**4 t Cl. Concentrations of most incompatible trace elements in the melt inclusions are close to those in the rocks and to the expected fractional differentiation trend. Melt inclusions in plagioclase were found to be selectively enriched in Li. The Li-enriched plagioclase with melt inclusions thought to originate from cumulate layers in the feeding system beneath Karymsky volcano, in which plagioclase interacted with Li-rich melts/brines and was subsequently entrapped and entrained by the magma during the 1996 eruption.