Desorptioilmanpainefotoionisaatio- ja desorptiosähkösumutusionisaatio-massaspektrometria lipidien analytiikassa

Lipidit ovat rasvaliukoisia kudoksesta peräisin olevia yhdisteitä, joilla on monia eri fysiologisia tehtäviä. Lipidien analyysimenetelmien kehittämien on tärkeää, sillä niiden esiintymistä elimistössä voidaan käyttää biomarkkerina sairauksien diagnostiikassa ja apuna sairauksien kehittymismekanismien tutkimisessa. Lipideihin kuuluu polaarisuudeltaan ja rakenteeltaan hyvin erilaisia yhdisteitä. Niiden massaspektrometria-analytiikassa on aikaisemmin käytetty useita erilaisia ionisaatiomenetelmiä, jotka vaativat näytteen esikäsittelyn ennen analyysia. Desorptiosähkösumutusionisaatio-massaspektrometria (DESI-MS) ja desorptio-ilmanpainefotoionisaatio-massaspektrometria (DAPPI-MS) ovat uusia ionisaatio-menetelmiä, jotka mahdollistavat yhdisteiden analysoinnin suoraan eri matriiseista, kuten kudosnäytteistä, usein ilman esikäsittelyä. DESI-MS soveltuu parhaiten suhteellisen polaaristen yhdisteiden analytiikkaan, kun taas DAPPI:lla voidaan ionisoida myös poolittomia yhdisteitä. DESI-MS:lla on jo aikaisemmin analysoitu erilaisia lipidejä, kun taas DAPPI-MS:lla on aikaisemmin analysoitu vain steroideja. DAPPI- ja DESI-MS:lla tutkittiin erilaisten lipidien (fosfolipidit, triglyseridit, rasvahapot, rasvaliukoiset vitamiinit ja steroidit) ionisoitumista. Molemmilla menetelmillä optimoitiin standardiyhdisteille mittausolosuhteet. Lipidejä analysoitiin myös suoraan farmaseuttisista valmisteista. DAPPI:n ja DESI:n soveltuvuudessa erilaisten lipidien ionisoimiseen oli jonkin verran eroja. DAPPI toimi hyvin varsinkin poolittomampien lipidien, eli triglyseridien, steroidien, vitamiinien ja rasvahappojen ionisaatiossa, mutta huonosti hieman polaarisempien ja herkästi hajoavien fosfolipidien ionisaatiossa. Fosfolipidit fragmentoituivat DAPPI-ionisaatiossa, eikä moolimassatiedon sisältävää ionia saatu näkyviin. DESI puolestaan toimii hyvin fosfolipidien ionisoimisessa ja melko hyvin myös muiden tutkittavien lipidien ionisoimisessa, lukuunottamatta kaikkein poolittomimpia lipidejä. Uutta tietoa tutkimuksessa saatiin varsinkin DAPPI:n soveltuvuudesta erilaisten lipidien analytiikkaan. Tulosten perusteella voidaan sanoa, että DAPPI toimii yhtä hyvin tai jopa DESI:a paremmin useiden eri lipidien analytiikkassa. Menetelmää tulisi kuitenkin kehittää edelleen, jotta fosfolipidien, jotka ovat elimistön tärkeä lipidiryhmä, analysointi onnistuisi DAPPI:lla. Työssä ei analysoitu lipidejä suoraan kudosnäytteestä, joten DAPPI:n soveltuvuudesta lipidien analysointiin suoraan kudosnäytteistä ei voida tehdä johtopäätöksiä tämän työn perusteella.

浅论实现基于MapX的灌溉信息系统的关键技术

现代化的灌溉用水管理是实现农业高效用水的重要措施之一,它可实现灌溉水资源的合理配置和灌溉系统的优化调度,达到节水增产目的,使有限的水资源获得最大的效益。采用手工方式进行灌溉用水管理,难以及时提供水资源利用最优化方案,因此急需研制出具有网络通信功能的可视化操作界面的灌溉信息管理系统,为灌区水资源评价和利用、规划等工作奠定良好的数据基础。GIS不仅具有强大的空间数据管理功能,还具有丰富的多元地学数据分析处理能力和直观的图形显示效果,因此利用GIS进行灌区的管理与建设将会有效提高灌区的工作效率和经济效益。笔者在实践调研的基础上,根据灌溉信息管理系统的功能规划及结构设计,利用MapX组件工具开发了陕西省冯家山灌区灌溉信息系统,对提高灌溉用水的管理效率进行了实例尝试,并着重对下列关键技术的运用进行了实践与思考:(1)阐述了利用可视化编程工具结合数据库管理技术、地理信息系统组件技术、网络通信技术等进行系统开发的过程;(2)着重介绍了基于MapX组件的空间数据库的建立与关联技术、灌溉管理信息的网络通信实现技术;(3)最后对在灌溉管理工作中运用GIS技术进行科学管理等相关问题进行了有益的探讨。

Christological personal seals and Christocentric devotion in later medieval England and Wales

New, E. (2002). Christological personal seals and Christocentric devotion in later medieval England and Wales. Antiquaries Journal. 82, pp.47-68. RAE2008

Diversité des champignons endophytes mycorhiziens et de classe II chez le pois chiche, et influence du génotype de la plante

réalisé en cotutelle avec la Faculté des Sciences de Tunis, Université Tunis El Manar.

Diversity and nutritional properties of Pakistani dates: implications for sustainable value chain and decent living perspectives of rural households

Date palm (Phoenix dactylifera L.) occupies almost three percent of the total worldwide cultivated area, with an annual production of seven million tonnes (t). Pakistan is an ideal place for the cultivation of date palm due to its sandy loam soil and semi-arid climate. In 2012, Pakistan produced 600,000 t of dates, on an area of 95,000 ha. Baluchistan province is the country’s top date producer, followed by Sindh, Punjab and Khyber Pakhtunkhwa (KPK) provinces. More than 300 date varieties are known to exist in Pakistan and some commercially important cultivars are: Karbalaen, Aseel, Muzawati, Fasli, Begum Jhangi, Hillawi, Dashtiari, Sabzo, Koharaba, Jaan Swore, Rabai and Dhakki. Six districts from the four provinces of Pakistan (Jhang, Muzaffargarh and Bahawalpur (Punjab), Dera Ismail Khan (KPK), Khairpur (Sindh) and Panjgur (Baluchistan)) with largest area under date palm cultivation were selected to conduct socio-economic surveys including the income sources of date palm growers. A structured questionnaire with open-ended and closed questions was used for face-to-face interviews of 170 date palm growers. At each location after selection of a first farmer through a local guide, the former was requested to provide names and addresses of three other date growers in his area. From these three names, one was randomly selected for the next sampling. Additionally, date palm fronds and fruits of all available cultivars were collected for morphological and nutritional analyses. Soil samples were collected from the groves for subsequent chemical and physical analyses. Almost all farmers used dates as a food item for their families and some were using low quality dates as a feed for their livestock. Apart from dates, other date palm components (trunk, spadix, frond, inflorescence and seed) were used by date palm growers as a raw material for making many by-products for their families. Date palm had a major contribution in the income of households, 24% received 91-100% of their income from date palms. More than half of the surveyed farmers had date palm groves, but scattered plantations, home gardens and intercropping systems with cereal and other fruits were also present. Dhakki, Muzawati, Aseel, and Karbalaen were the most important commercial cultivars grown in the provinces of KPK, Baluchistan, and Sindh. Aseel, Karoch, Haleni, Karbalaen, and Muzawati cultivars had the most firm fruit and good total soluble sugar, calcium and magnesium contents. The amount of magnesium found in dates of studied cultivars ranged from 0.143 to 0.876 mg g-1. A great variation in frond morphology was recorded among the cultivars. Fruit length and fruit weight was highest in Dhakki date, making it visually more attractive for customers in addition to its good nutritional properties. The seed weight of the studied cultivars ranged from 0.7-2.0 g, while Desi dates had largest seed, making them less attractive for marketing. However, in terms of nutritional value and fruit size, most of the investigated varieties can compete with globally important commercial dates.

A materailidade no caminho da efetivação do Espírito na Filosofia de Hegel

Hegel’s identification with idealism may not apprehend adequately his philosophical thinking if one takes it as a definitive and absolute determination because he is a dialectical thinker or even better speculative. In this sense the moment of materiality cannot be just put aside as a contingency but it is more the opposition through which the spirit fulfills itself. This one cannot be what it is without assuming the materiality as well as the matter cannot be effective without being overtaken in the spirit. The totality appointed by Hegel in the absolute spirit means precisely to know and to recognize one another in the other and also by the other as itself. The spirit only raises to itself insofar it assumes its opposition in matter and by being determined it determines itself but this cannot be fulfilled anywhere but in the matter. In the same way the matter cannot be effective without going beyond itself or being considered in thought, that is not as well establishing itself. If the spirit and the matter are effective insofar they are in relation with one another then the primacy of one over the other can only be understood as a result and not as a starting point. In this way the first moment must not be taken as something static but as coming to be.

Caracterização por espectrometria de massas e investigação das atividades anti-inflamatória e gastroprotetora do extrato etanólico e diterpenos clerodânicos de folhas de Casearia sylvestris Swartz

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Caracterização por espectrometria de massas e investigação das atividades anti-inflamatória e gastroprotetora do extrato etanólico e diterpenos clerodânicos de folhas de Casearia sylvestris Swartz

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Narodny opovydanni a /

Errata included.

Biblīografīi͡a sochinenīĭ Nikolai͡a Semenovicha Li͡eskova, s nachala ego literaturnoĭ di͡ei͡atelʹnosti - 1860 g. po 1887 g. (vkli͡uchitelʹno)

"V prodazhu postupilo pi͡atʹdesi͡at ėkzempli͡arov."

Istoricheskīe materīaly o t︠s︡erkvakh i selakh XVI-XVIII st.

Includes bibliographical references.

A study of methods used to analyze total oil and polycyclic aromatic hydrocarbons in produced water: steps towards the validation of molecularly imprinted polymers for use in marine environmetns

Produced water is a by-product of offshore oil and gas production, and is released in large volumes when platforms are actively processing crude oil. Some pollutants are not typically removed by conventional oil/water separation methods and are discharged with produced water. Oil and grease can be found dispersed in produced water in the form of tiny droplets, and polycyclic aromatic hydrocarbons (PAHs) are commonly found dissolved in produced water. Both can have acute and chronic toxic effects in marine environments even at low exposure levels. The analysis of the dissolved and dispersed phases are a priority, but effort is required to meet the necessary detection limits. There are several methods for the analysis of produced water for dispersed oil and dissolved PAHs, all of which have advantages and disadvantages. In this work, EPA Method 1664 and APHA Method 5520 C for the determination of oil and grease will be examined and compared. For the detection of PAHs, EPA Method 525 and PAH MIPs will be compared, and results evaluated. APHA Method 5520 C Partition-Infrared Method is a liquid-liquid extraction procedure with IR determination of oil and grease. For analysis on spiked samples of artificial seawater, extraction efficiency ranged from 85 – 97%. Linearity was achieved in the range of 5 – 500 mg/L. This is a single-wavelength method and is unsuitable for quantification of aromatics and other compounds that lack sp³-hybridized carbon atoms. EPA Method 1664 is the liquid-liquid extraction of oil and grease from water samples followed by gravimetric determination. When distilled water spiked with reference oil was extracted by this procedure, extraction efficiency ranged from 28.4 – 86.2%, and %RSD ranged from 7.68 – 38.0%. EPA Method 525 uses solid phase extraction with analysis by GC-MS, and was performed on distilled water and water from St. John’s Harbour, all spiked with naphthalene, fluorene, phenanthrene, and pyrene. The limits of detection in harbour water were 0.144, 3.82, 0.119, and 0.153 g/L respectively. Linearity was obtained in the range of 0.5-10 g/L, and %RSD ranged from 0.36% (fluorene) to 46% (pyrene). Molecularly imprinted polymers (MIPs) are sorbent materials made selective by polymerizing functional monomers and crosslinkers in the presence of a template molecule, usually the analytes of interest or related compounds. They can adsorb and concentrate PAHs from aqueous environments and are combined with methods of analysis including GC-MS, LC-UV-Vis, and desorption electrospray ionization (DESI)- MS. This work examines MIP-based methods as well as those methods previously mentioned which are currently used by the oil and gas industry and government environmental agencies. MIPs are shown to give results consistent with other methods, and are a low-cost alternative improving ease, throughput, and sensitivity. PAH MIPs were used to determine naphthalene spiked into ASTM artificial seawater, as well as produced water from an offshore oil and gas operation. Linearity was achieved in the range studied (0.5 – 5 mg/L) for both matrices, with R² = 0.936 for seawater and R² = 0.819 for produced water. The %RSD for seawater ranged from 6.58 – 50.5% and for produced water, from 8.19 – 79.6%.

Analysis of bio-derived platform chemicals in ionic liquid media by desorption/ionization mass spectrometry

In this work, desorption/ionization mass spectrometry was employed for the analysis of sugars and small platform chemicals that are common intermediates in biomass transformation reactions. Specifically, matrix-assisted laser desorption/ionization (MALDI) and desorption electrospray ionization (DESI) mass spectrometric techniques were employed as alternatives to traditional chromatographic methods. Ionic liquid matrices (ILMs) were designed based on traditional solid MALDI matrices (2,5-dihydroxybenzoic acid (DHB) and α-cyano-4-hydroxycinnamic acid (CHCA)) and 1,3-dialkylimidazolium ionic liquids ([BMIM]Cl, [EMIM]Cl, and [EMIM]OAc) that have been employed as reaction media for biomass transformation reactions such as the conversion of carbohydrates to valuable platform chemicals. Although two new ILMs were synthesized ([EMIM][DHB] and [EMIM][CHCA] from [EMIM]OAc), chloride-containing ILs did not react with matrices and resulted in mixtures of IL and matrix in solution. Compared to the parent solid matrices, much less matrix interference was observed in the low mass region of the mass spectrum (< 500 Da) using each of the IL-matrices. Furthermore, the formation of a true ILM (i.e. a new ion pair) does not appear to be necessary for analyte ionization. MALDI sample preparation techniques were optimized based on the compatibility with analyte, IL and matrix. ILMs and IL-matrix mixtures of DHB allowed for qualitative analysis of glucose, fructose, sucrose and N-acetyl-D-glucosamine. Analogous CHCA-containing ILMs did not result in appreciable analyte signals under similar conditions. Small platform compounds such as 5-hydroxymethylfurfural (HMF) and levulinic acid were not detected by direct analysis using MALDI-MS. Furthermore, sugar analyte signals were only detected at relatively high matrix:IL:analyte ratios (1:1:1) due to significant matrix and analyte suppression by the IL ions. Therefore, chemical modification of analytes with glycidyltrimethylammonium chloride (GTMA) was employed to extend this method to quantitative applications. Derivatization was accomplished in aqueous IL solutions with fair reaction efficiencies (36.9 – 48.4 % glucose conversion). Calibration curves of derivatized glucose-GTMA yielded good linearity in all solvent systems tested, with decreased % RSDs of analyte ion signals in IL solutions as compared to purely aqueous systems (1.2 – 7.2 % and 4.2 – 8.7 %, respectively). Derivatization resulted in a substantial increase in sensitivity for MALDI-MS analyses: glucose was reliably detected at IL:analyte ratios of 100:1 (as compared to 1:1 prior to derivatization). Screening of all test analytes resulted in appreciable analyte signals in MALDI-MS spectra, including both HMF and levulinic acid. Using appropriate internal standards, calibration curves were constructed and this method was employed for monitoring a model dehydration reaction of fructose to HMF in [BMIM]Cl. Calibration curves showed wide dynamic ranges (LOD – 100 ng fructose/μg [BMIM]Cl, LOD – 75 ng HMF/μg [BMIM]Cl) with correlation coefficients of 0.9973 (fructose) and 0.9931 (HMF). LODs were estimated from the calibration data to be 7.2 ng fructose/μg [BMIM]Cl and 7.5 ng HMF/μg [BMIM]Cl, however relatively high S/N ratios at these concentrations indicate that these values are likely overestimated. Application of this method allowed for the rapid acquisition of quantitative data without the need for prior separation of analyte and IL. Finally, small molecule platform chemicals HMF and levulinic acid were qualitatively analyzed by DESI-MS. Both HMF and levulinic acid were easily ionized and the corresponding molecular ions were easily detected in the presence of 10 – 100 times IL, without the need for chemical modification prior to analysis. DESI-MS analysis of ILs in positive and negative ion modes resulted in few ions in the low mass region, showing great potential for the analysis of small molecules in IL media.