红枫湖溶解有机质的分离富集、地球化学特征和环境效应

作为全球碳循环的主要组成部分，溶解有机质在水生生态系统的各种物理、化学和生物过程中起着十分重要的作用：它是湖泊异养型生物所需能量的主要提供者；是湖泊水体pH的调节剂和控制因素；能够与金属离子或有机污染物相互作用，从而影响它们的迁移转化、毒性和生物可利用性；溶解有机质也是饮用水氯化工艺中生成具有致癌作用消毒副产品的主要前驱物质。溶解有机质组成和结构十分复杂，一般由腐殖质和非腐殖质物质组成，相应的环境地球化学特征和行为也各不相同。因此，研究溶解有机质各分离组分的结构特征和环境效应，将有助于我们对溶解有机质复杂化学结构、循环特征及行为特征的深入理解；有助于揭示溶解有机质对环境中微量污染物的迁移、转化、毒性和生物有效性的影响机理和贡献因素；为水环境评价、预测、控制和管理提供科学依据。 本论文选择云贵高原山区湖泊—红枫湖为研究对象，利用XAD树脂分离技术，把湖泊水体中溶解有机质按极性的不同分成了疏水性酸、碱、中性物质和亲水性酸、碱、中性物质等六种有机组分。主要运用元素分析、有机碳分析仪、傅立叶变换红外光谱、紫外－可见分光光度，高效液相体积排阻色谱、三维荧光光谱和稳定同位素质谱仪等现代分析方法和手段，对各有机组分的地球化学特征及来源的进行了表征和探讨。同时利用荧光猝灭滴定技术研究了溶解有机质分离组分与铜的相互作用，利用顶空气相色谱法测定了各分离组分与氯气反应活性的大小，并确立了生成消毒副产物的主要前驱物质。本论文的研究成果主要有以下几点： 1.改进了分离流程：在XAD－8树脂分离溶解有机质流程的基础上，引入XAD－4树脂，对贵州红枫湖水体中溶解有机质进行了富集分离，得腐殖酸、富里酸、疏水性中性物质、亲水性酸、亲水性碱、亲水性中性物质等六种有机组分，回收率为82%。各分离组分的组成与其它天然水体的组成接近，其中以富里酸为主，占分离组分的51%。 2.溶解有机质分离组分化学结构特征的研究：元素分析表明疏水性组分具有较高的碳和硫含量，而亲水性组分O/C比较高，含有较多的含氧官能团；傅立叶变换红外光谱表明各分离组分在3424－3434 cm-1具有O-H和N-H的吸收峰，腐殖酸组分主要为含氮和聚糖物质，富里酸和亲水性酸表现强的羧基吸收峰。高效体积排阻色谱表明各六种有机组分的分子量较小，重均(Mw)和数均(Mn)分子量分别集中在1688-2355Da和1338-1928Da之间，其中Mw和紫外吸收比值(E2/E3)之间呈负相关关系；三维荧光光谱显示六种有机组分表现了4种不同类型的荧光峰，紫外区类富里酸荧光峰peakA和可见区类富里酸荧光峰peakC；疏水性中性物质还表现了两种类蛋白荧光峰peakB和peakD。荧光强度与紫外吸光系数SUVA254之间呈显著正相关关系，说明了产生荧光和紫外的物质具有某些相似的官能团，其中芳香官能团和共轭双键在这两类光谱的产生中具有重要作用。本研究进一步揭示了溶解有机质不同有机组分的分子量分布、荧光光谱特征和紫外吸收特征之间的一致性，反映了各有机组分之间的亲水、疏水与分子量、光谱特征之间的内在联系，本研究有助于加我们深对溶解有机质复杂性和相似性及化学结构与行为的进一步认识。 3.溶解有机质分离组分来源问题的探讨：我们利用δ13C及C/N比值并结合荧光光谱特征来指示溶解有机质的来源。各分离组分的δ13C及C/N比值表明富里酸主要来自陆源C3植被形成的土壤有机质，而腐殖酸、疏水性中性物质、亲水性酸、亲水性碱、亲水性中性物质属于陆源和内源的混合来源，其中腐殖酸、亲水性酸、亲水性碱接近红枫湖藻类一端，而疏水性中性物质和亲水性中性物质接近陆源一端。荧光光谱表明疏水性中性物质中含有类蛋白荧光峰，可能暗示了该组分还与人类活动有关。该研究加深了对溶解有机质来源的多样性和影响因素复杂性的认识。 4.溶解有机质分离组分与铜离子的相互作用，利用荧光猝灭滴定技术研究了分离组分与铜离子的相互作用，结果表明溶解有机质滴加铜离子后荧光强调显著降低，同时发射波长Em发生蓝移，而激发波长Ex基本不变，说明了分离有机组分在与铜离子相互作用后，π电子减少，共轭性和芳香型降低，直线型分子向非直线型分子转变；溶解有机质分离组分与铜相互作用的滴定曲线与修正的Stern-Volmer模型十分吻合；分离组分的稳定常数logK介于4.73-5.16之间（C峰）和4.64-5.24之间（A峰），logKA与logKC与总酸度以及与酚羟基之间存在显著相关性, 与羧基含量之间也有弱相关关系，说明铜离子优先与配体中强配位点（酚羟基）络合，其次为弱配位基（羧基）。该研究揭示了云贵高原山区湖泊溶解有机质分离组分与金属离子相互作用的差异性和影响因素，为水环境中金属离子迁移转化和毒性的评价提供理论依据。 5.溶解有机质分离组分卤代活性的比较：我们运用顶空气相色谱法测定了红枫湖分离组分与消毒剂反应生成有机卤代物的情况。结果表明红枫湖分离组分氯化消毒副产物主要以三氯甲烷(CHCl3)和二溴一氯甲烷(CHBr2Cl)为主，富里酸是生成三卤甲烷的主要前驱物质，同时富里酸的卤代反应活性也最强。该研究揭示了云贵高原山区湖泊中富里酸是生成消毒副产物的主要前驱物质，该组分以陆源有机质输入为主。因此，该研究对饮用水消毒具有一定的现实意义。

中老年男性性激素水平与认知功能的关系

Abstract Objective: Study the relationship between sex hormones and cognitive function in aged male. Methods: The serum sex hormones including Free Testosterone(FT), Total Testosterone(TT), Estradiol(E2), Prolactin(PRL) and Luteotropic Hormone(LH) of 74 elderly men(47-75 years old, mean 58.73) were measured by radioimmunoassay. They were all applied the cognitive tests of episodic memory and verbal fluency. For the episodic memory, four experiments examined picture, digit and words memory separately. Four verbal fluency tests were performed in the middle of each episodic memory. The 74 men were divided into two groups according to the levels of their sex hormones respectively, with each group had 37 subjects. Data was analyzed by the software of SPSS 11.0. Results: Mean age and the mean years of formal education had no significant difference between the groups; Men in the group with higher levels of FT had significantly higher scores in the tests of picture memory and words memory；Men in the group with higher levels of TT had significantly higher scores in the tests of verbal fluency4, picture memory and words memory；Men in the group with higher levels of E2 had significantly higher scores in the tests of picture memory and verbal fluency3,4；There were no correlations between PRL or LH and the cognitive tests. Conclusions: 1 Sex hormones (especially FT, TT, E2) did have effect on the cognitive function in aged male, higher levels of hormones related with higher scores of some cognitive tests. 2 Among the cognitive functions, picture memory and words memory performance seemed being effected by the sex hormones most.

Cartas eruditas, y curiosas : en que, por la mayor parte se continua el designio del Teatro Critico Universal, impugnando, ó reduciendo á dudosas varias opiniones comunes

Nueva impresion.

Targeting the EP1 receptor reduces Fas ligand expression and increases the antitumor immune response in an in vivo model of colon cancer

Despite studies demonstrating that inhibition of cyclooxygenase-2 (COX-2)-derived prostaglandin E2 (PGE2) has significant chemotherapeutic benefits in vitro and in vivo, inhibition of COX enzymes is associated with serious gastrointestinal and cardiovascular side effects, limiting the clinical utility of these drugs. PGE2 signals through four different receptors (EP1–EP4) and targeting individual receptor(s) may avoid these side effects, while retaining significant anticancer benefits. Here, we show that targeted inhibition of the EP1 receptor in the tumor cells and the tumor microenvironment resulted in the significant inhibition of tumor growth in vivo. Both dietary administration and direct injection of the EP1 receptor-specific antagonist, ONO-8713, effectively reduced the growth of established CT26 tumors in BALB/c mice, with suppression of the EP1 receptor in the tumor cells alone less effective in reducing tumor growth. This antitumor effect was associated with reduced Fas ligand expression and attenuated tumor-induced immune suppression. In particular, tumor infiltration by CD4+CD25+Foxp3+ regulatory T cells was decreased, whereas the cytotoxic activity of isolated splenocytes against CT26 cells was increased. F4/80+ macrophage infiltration was also decreased; however, there was no change in macrophage phenotype. These findings suggest that the EP1 receptor represents a potential target for the treatment of colon cancer.

Investigation of polyhydroxyalkanoate production by an activated sludge microbial consortium treating artificial dairy wastewater

Petrochemical plastics/polymers are a common feature of day to day living as they occur in packaging, furniture, mobile phones, computers, construction equipment etc. However, these materials are produced from non-renewable materials and are resistant to microbial degradation in the environment. Considerable research has therefore been carried out into the production of sustainable, biodegradable polymers, amenable to microbial catabolism to CO2 and H2O. A key group of microbial polyesters, widely considered as optimal replacement polymers, are the Polyhydroxyalkaonates (PHAs). Primary research in this area has focused on using recombinant pure cultures to optimise PHA yields, however, despite considerable success, the high costs of pure culture fermentation have thus far hindered the commercial viability of PHAs thus produced. In more recent years work has begun to focus on mixed cultures for the optimisation of PHA production, with waste incorporations offering optimal production cost reductions. The scale of dairy processing in Ireland, and the high organic load wastewaters generated, represent an excellent potential substrate for bioconversion to PHAs in a mixed culture system. The current study sought to investigate the potential for such bioconversion in a laboratory scale biological system and to establish key operational and microbial characteristics of same. Two sequencing batch reactors were set up and operated along the lines of an enhanced biological phosphate removal (EBPR) system, which has PHA accumulation as a key step within repeated rounds of anaerobic/aerobic cycling. Influents to the reactors varied only in the carbon sources provided. Reactor 1 received artificial wastewater with acetate alone, which is known to be readily converted to PHA in the anaerobic step of EBPR. Reactor 2 wastewater influent contained acetate and skim milk to imitate a dairy processing effluent. Chemical monitoring of nutrient remediation within the reactors as continuously applied and EBPR consistent performances observed. Qualitative analysis of the sludge was carried out using fluorescence microscopy with Nile Blue A lipophillic stain and PHA production was confirmed in both reactors. Quantitative analysis via HPLC detection of crotonic acid derivatives revealed the fluorescence to be short chain length Polyhydroxybutyrate, with biomass dry weight accumulations of 11% and 13% being observed in reactors 1 and 2, respectively. Gas Chromatography-Mass Spectrometry for medium chain length methyl ester derivatives revealed the presence of hydroxyoctanoic, -decanoic and -dodecanoic acids in reactor 1. Similar analyses in reactor 2 revealed monomers of 3-hydroxydodecenoic and 3-hydroxytetradecanoic acids. Investigation of the microbial ecology of both reactors as conducted in an attempt to identify key species potentially contributing to reactor performance. Culture dependent investigations indicated that quite different communities were present in both reactors. Reactor 1 isolates demonstrated the following species distributions Pseudomonas (82%), Delftia acidovorans (3%), Acinetobacter sp. (5%) Aminobacter sp., (3%) Bacillus sp. (3%), Thauera sp., (3%) and Cytophaga sp. (3%). Relative species distributions among reactor 2 profiled isolates were more evenly distributed between Pseudoxanthomonas (32%), Thauera sp (24%), Acinetobacter (24%), Citrobacter sp (8%), Lactococcus lactis (5%), Lysinibacillus (5%) and Elizabethkingia (2%). In both reactors Gammaproteobacteria dominated the cultured isolates. Culture independent 16S rRNA gene analyses revealed differing profiles for both reactors. Reactor 1 clone distribution was as follows; Zooglea resiniphila (83%), Zooglea oryzae (2%), Pedobacter composti (5%), Neissericeae sp. (2%) Rhodobacter sp. (2%), Runella defluvii (3%) and Streptococcus sp. (3%). RFLP based species distribution among the reactor 2 clones was as follows; Runella defluvii (50%), Zoogloea oryzae (20%), Flavobacterium sp. (9%), Simplicispira sp. (6%), Uncultured Sphingobacteria sp. (6%), Arcicella (6%) and Leadbetterella bysophila (3%). Betaproteobacteria dominated the 16S rRNA gene clones identified in both reactors. FISH analysis with Nile Blue dual staining resolved these divergent findings, identifying the Betaproteobacteria as dominant PHA accumulators within the reactor sludges, although species/strain specific allocations could not be made. GC analysis of the sludge had indicated the presence of both medium chain length as well short chain length PHAs accumulating in both reactors. In addition the cultured isolates from the reactors had been identified previously as mcl and scl PHA producers, respectively. Characterisations of the PHA monomer profiles of the individual isolates were therefore performed to screen for potential novel scl-mcl PHAs. Nitrogen limitation driven PHA accumulation in E2 minimal media revealed a greater propensity among isoates for mcl-pHA production. HPLC analysis indicated that PHB production was not a major feature of the reactor isolates and this was supported by the low presence of scl phaC1 genes among PCR screened isolates. A high percentage distribution of phaC2 mcl-PHA synthase genes was recorded, with the majority sharing high percentage homology with class II synthases from Pseudomonas sp. The common presence of a phaC2 homologue was not reflected in the production of a common polymer. Considerable variation was noted in both the monomer composition and ratios following GC analysis. While co-polymer production could not be demonstrated, potentially novel synthase substrate specificities were noted which could be exploited further in the future.

HPV16 antibodies as risk factors for oropharyngeal cancer and their association with tumor HPV and smoking status.

BACKGROUND: Antibodies (Abs) to the HPV16 proteome increase risk for HPV-associated OPC (HPVOPC). The goal of this study was to investigate the association of a panel of HPV16 Abs with risk for OPC as well as the association of these Abs with tumor HPV and smoking status among patients with OPC. METHODS: IgG Abs to the HPV16 antigens E1, E2, E4, E5, E6, E7, L1, L2 were quantified using a programmable ELISA assay. Sera were obtained from 258 OPC patients at diagnosis and 250 healthy controls. HPV16 tumor status was measured by PCR for 137 cases. Multivariable logistic regression was used to calculate odds ratios for the association of HPV16 Abs with risk for OPC. RESULTS: HPV16 E1, E2, E4, E5, E6, E7 and L1-specific IgG levels were elevated in OPC patients compared to healthy controls (p<0.05). After multivariable adjustment, Ab positivity for NE2, CE2, E6, and/or E7 was associated with OPC risk (OR [95% CI], 249.1 [99.3-624.9]). Among patients with OPC, Ab positivity for these antigens was associated with tumor HPV status, especially among never or light smokers (OR [95% CI], 6.5 [2.1-20.1] and OR [95% CI], 17.5 [4.0-77.2], respectively). CONCLUSIONS: Antibodies to HPV16 proteins are associated with increased risk for HPVOPC. Among patients with OPC, HPV16 Abs are associated with tumor HPV status, in particular among HPV positive patients with no or little smoking history.

Appropriateness of Largemouth Bass as a Model Species for Detection of Endocrine Dissruption

Intersex in largemouth bass (Micropterus salmoides) has been correlated with regional anthropogenic activity, but has not been causally linked to environmental factors. Four groups of hatchery-reared largemouth bass (LMB) and fathead minnows (FHM) of varying ages and sex were exposed to aqueous poultry litter mixtures, 17β- estradiol (E2), and controls. Water samples were analyzed for estrogens through liquid chromatography tandem mass spectrometry and estrogenicity through the bioluminescent yeast estrogen screen assay. Fish plasma was analyzed for the egg yolk protein vitellogenin (Vtg) using enzyme–linked immunosorbent assay and gonad tissue was examined histologically for enumeration of testicular oocytes (TO). Water chemistry revealed typical E2 conversion to Estrone with subsequent decay over the exposure periods. A modest prevalence of TO (9.4%) was detected with no apparent treatment effect. While significant Vtg induction was found in E2 exposed FHM, minimal Vtg induction was found in male LMB. Despite field findings of intersex in male LMB, this species may be poorly suited for laboratory investigations into endocrine disruption.

La geometría en el aula: una propuesta para la interpretación de conceptos e ideas matemáticas y físicas

El presente trabajo se desprende de la práctica docente que se está llevando a cabo en el Centro Educativo Femenino de Antioquia (CEFA) en la ciudad de Medellín con estudiantes del grado décimo, el cual tiene como intención primordial retornar la geometría al aula de clase como una herramienta que facilita la interpretación de las ideas matemáticas y físicas, empleando la metodología de aula-taller como fundamento para alcanzar tal fin. Hasta ahora se ha logrado despertar un relevante interés en el manejo del lenguaje geométrico y una mejor interpretación de algunos conceptos como el teorema de Pitágoras y el número Pi, a partir de uso del material concreto que ayuda al estudiante a alcanzar una mejor apropiación de dichos conceptos.

Partitioning, bioavailability and effects of oestrogens and xeno-oestrogens in the aquatic environment

This review provides insights into the distribution and impact of oestrogens and xeno-oestrogens in the aquatic environment and highlights some significant knowledge gaps in our understanding of endocrine disrupting chemicals. Key areas of uncertainty in the assessment of risk include the role of estuarine sediments in mediating the fate and bioavailability of environmental (xeno)oestrogens (notably their transfer to benthic organisms and estuarine food chains), together with evidence for endocrine disruption in invertebrate populations. Emphasis is placed on using published information to interpret the behaviour and effects of a small number of model compounds thought to contribute to oestrogenic effects in nature; namely, the natural steroid 17 beta -oestradiol (E2) and the synthetic hormone 17 alpha -ethinyloestradiol (EE2), together with the alkyl-phenols octyl- and nonyl-phenol (OP, NP) as oestrogen mimics. Individual sections of the review are devoted to sources and concentrations of (xeno)oestrogens in waterways, sediment partitioning and persistence, bioaccumulation rates and routes, assays and biomarkers of oestrogenicity, and, finally, a synopsis of reproductive and ecological effects in aquatic species.