Hyperpolarization-Enhanced NMR Spectroscopy of Unaltered Biofluids Using Photo-CIDNP

Altres ajuts: acords transformatius de la UABThe direct and unambiguous detection and identification of individual metabolite molecules present in complex biological mixtures constitute a major challenge in (bio)analytical research. In this context, nuclear magnetic resonance (NMR) spectroscopy has proven to be particularly powerful owing to its ability to provide both qualitative and quantitative atomic-level information on multiple analytes simultaneously in a noninvasive manner. Nevertheless, NMR suffers from a low inherent sensitivity and, moreover, lacks selectivity regarding the number of individual analytes to be studied in a mixture of a myriad of structurally and chemically very different molecules, e.g., metabolites in a biofluid. Here, we describe a method that circumvents these shortcomings via performing selective, photochemically induced dynamic nuclear polarization (photo-CIDNP) enhanced NMR spectroscopy on unmodified complex biological mixtures, i.e., human urine and serum, which yields a single, background-free one-dimensional NMR spectrum. In doing this, we demonstrate that photo-CIDNP experiments on unmodified complex mixtures of biological origin are feasible, can be performed straightforwardly in the native aqueous medium at physiological metabolite concentrations, and act as a spectral filter, facilitating the analysis of NMR spectra of complex biofluids. Due to its noninvasive nature, the method is fully compatible with state-of-the-art metabolomic protocols providing direct spectroscopic information on a small, carefully selected subset of clinically relevant metabolites. We anticipate that this approach, which, in addition, can be combined with existing high-throughput/high-sensitivity NMR methodology, holds great promise for further in-depth studies and development for use in metabolomics and many other areas of analytical research

Credible and Actionable Evidence Across Stakeholder Levels of the Cooperative Extension System

This article provides a look at the various levels within the Cooperative Extension System and the use of evidence within these levels. The authors examine the factors associated with credible evidence and the various levels. The impact of factors such as politics, science, stakeholder support, and expectations are discussed. The various levels within Extension are summarized in relation to evidence that is routinely requested or required for each. Lastly, the authors use information directly from Extension directors to provide a framework for the discussion

Design of Zn-, Cu-, and Fe-Coordination Complexes Confined in a Self-Assembled Nanocage

The encapsulation of coordination complexes in a tetragonal prismatic nanocage (1·(BArF)8) built from Zn-porphyrin and macrocyclic Pd-clip-based synthons is described. The functional duality of the guest ligand L1 allows for its encapsulation inside the cage 1·(BArF)8, along with the simultaneous coordination of ZnII, CuII, or FeIII metal ions. Remarkably, the coordination chemistry inside the host–guest adduct L1⊂1·(BArF)8 occurs in both solution solution and solid state. The resulting confined metallocomplexes have been characterized by means of UV-vis, ESI-HRMS, NMR, and EPR techniques. Furthermore, the emission of the Zn-porphyrin fluorophores of 1·(BArF)8 is strongly quenched by the encapsulation of paramagnetic complexes, representing a remarkable example of guest-dependent tuning of the host fluorescence

Re-esterified Palm Oils, Compared to Native Palm Oil, do not Alter Fat Absorption, Postprandial Lipemia or Growth Performance in Broiler Chicks

Re-esterified palm oils are obtained from the chemical esterification of palm acid oils (rich in free fatty acids) with glycerol, both economically interesting by-products from oil refining and biodiesel industries, respectively. Thus, re-esterified palm oils could be an economically interesting alternative to native palm oil in broiler chick diets. However, because they may have different physicochemical properties than have their corresponding native oil, we assessed the effect of fatty acid (FA) positional distribution within acylglycerol molecules and the effect of acylglycerol composition on FA apparent absorption, and their possible consequences on the evolution of postprandial lipemia and growth performance in broiler chicks. Seventy-two 1-day-old female broiler chicks were randomly distributed into 18 cages. The three treatments used were the result of a basal diet supplemented with 6 wt% of native palm oil (N-TAG), re-esterified palm oil (E-TAG), or re-esterified palm oil high in mono- and diacylglycerols (E-MDAG). Chemical esterification raised the fraction of palmitic acid at the sn -2 position from 9.63 mol% in N-TAG oil to 17.9 mol% in E-TAG oil. Furthermore, E-MDAG oil presented a high proportion of mono- (23.1 wt%) and diacylglycerols (51.2 wt%), with FA mainly located at the sn -1,3 positions, which resulted in a lower gross-energy content and an increased solid-fat index at the chicken's body temperature. However, re-esterified palm oils did not alter fat absorption, postprandial lipemia, or growth performance, compared to native palm oil, so they can be used as alternative fat sources in broiler chick diets

Procedures and types of small wastewater treatment plants

Zmes vodika in kisika, imenovana voda, je ključni in nenadomestljiv element za življenje. Najdemo jo namreč v vseh živih bitjih, omogoča delovanje vseh življenjsko pomembnih procesov v organizmu, poleg tega z njo zadovoljujemo naše fiziološke potrebe, vzdržujemo čistočo, higieno in jo uporabljamo za najrazličnejše tehnološke namene. Vsak od nas v povprečju porabi kar 150 litrov vode na dan, kar pomeni, da pride do velikih količin odpadne vode. Vso to vodo je potrebno pred ponovno uporabo, izpustom v tla ali v odprte vodotoke prečistiti. Za to poskrbi človek s pospešenim in kontroliranim procesom čiščenja s pomočjo BIOLOŠKIH ČISTILNIH NAPRAV. V prvem delu diplomske naloge so predstavljeni vsi postopki in vrste malih čistilnih naprav, ki se uporabljajo za čiščenje odpadnih voda do 2000 PE (populacijski ekvivalent). Na kratko je opisana tudi aktualna zakonodaja, ki predpisuje kako je/bo potrebno urediti čiščenje odpadnih voda. V drugem delu diplomske naloge sem v poplavi ponudnikov malih čistilnih naprav, ki jih je zaradi aktualnosti le-teh vse več, poskušal čim bolj sistematično pregledati tržišče v republiki Sloveniji. Prav tako sem pregledal tudi cenovne razrede malih čistilnih naprav 5–100 PE in poizkušal ugotoviti najbolj ekonomične rešitve za dane situacije.A mixture of hydrogen and oxygen called water is the key and irreplaceable element for life. We find it in all living creatures and it enables the activity of all vital processes in the organism. Besides, with water we satisfy our physiological needs, we keep everything clean and hygienic and we also use it for different technical purposes. Each of us spends around 150 liters of water per day, which means that there is a lot of »wastewater«. All of this water has to be cleaned before another use, release into the soil or in the open watercourses. The cleaning provides a man with an accelerated and controlled cleaning process using biological wastewater treatment plant. In the first part of my diploma there are presented all the procedures and types of small wastewater treatment plants, which are used for wastewater treatment up to 2000 PE (population equivalent). Briefly is also described the current law, which prescribes how it is or will be necessary to regulate wastewater treatment. In the second part of the diploma I tried to systematically examine the market in the Republic of Slovenia. I have also reviewed the price brackets of small wastewater treatment plants from 5-100 PE and tried to find the most economical solutions for a given situation

Social times, reproduction and social inequality at work : contrasts and comparative perspectives between countries

Production of INCASI Project H2020-MSCA-RISE-2015 GA 691004If the focus is placed specifically on the problem of work and family, the daily life of people and their use of time are a main problem. This time is expressed in both freely available time, which is related to activities, and time of the productive and reproductive sphere. This chapter considers work in a broad sense and takes into account the sexual division of labour. Specifically, this chapter will explore transformations in time use and social inequality in unpaid work. For this purpose, a comparative analysis of time-use surveys will be used, analysing the time spent, and the time dedicated to household chores in Chile, Argentina, Uruguay and Spain. From an analytical viewpoint, the analysis will place social reproduction at the centre of the socio-economic system, showing that the economic crisis has affected women and men differently, and that in both Europe and Latin America the family pattern is being replaced by a dominant family model of a male provider and a double presence of women. The large-scale incorporation of women into the labour market has emphasised the role that women assume in the domestic sphere perpetuating gender segregation in employment and in domestic and care work

The possible role of local air pollution in climate change in West Africa

The climate of West Africa is characterized by a sensitive monsoon system that is associated with marked natural precipitation variability. This region has been and is projected to be subject to substantial global and regional-scale changes including greenhouse-gas-induced warming and sea-level rise, land-use and land-cover change, and substantial biomass burning. We argue that more attention should be paid to rapidly increasing air pollution over the explosively growing cities of West Africa, as experiences from other regions suggest that this can alter regional climate through the influences of aerosols on clouds and radiation, and will also affect human health and food security. We need better observations and models to quantify the magnitude and characteristics of these impacts

Substitution reactions on cyclometalated Pt(IV) complexes. Associative tuning by fluoro Ligands and fluorinated substituents

The substitution reactions of sulfide by phosphines on Pt(IV) complexes having a cyclometalated imine ligand, two methyl groups in a cis geometrical arrangement, and a halogen and a sulfide as ligands, [Pt (Me)(2)X(CN)(SR2)], have been studied as a function of temperature, solvent, and electronic and steric characteristics of the phosphines, sulfides, X-1 and CN. In most of these cases, a limiting dissociative mechanism has been found, where the dissociation of the sulfide ligand corresponds to the rate-determining step. The intermediate species formed behaves as a true pentacoordinated Pt(IV) compound in a steady-state concentration only for the systems with SMe2; for the bulkier SEt2 and SBzl(2) leaving ligands the rate constants and activation parameters show an important degree of solvent dependence, which correlates with the ability of the solvent to form hydrogen bonds, The X-ray crystal structure of one of the dibenzyl sulfide complexes has been determined, and the geometrical arrangement of the ligands has been determined by NOE NMR measurements at low temperature. The nature of the solvent, imine, sulfide, and halogen ligands produces differences in the reaction rates, which can be quantified very well by the corresponding AS' values that move from +48 to -90 J K-1 mol(-1). The reaction on [Pt(Me)(2)F(C-5(C) under barF(4)CH (N) under bar CH2Ph) (SME2)] has been found to take place via a mechanism that depends strongly on the bulkiness of the substituting phosphine, While for PCy3 the reaction is dissociative, for smaller entering ligands the first associatively activated substitution mechanisms on organometallic Pt(IV) complexes have been established with values of DeltaH(double dagger) and DeltaS(double dagger) in the 28-44 kJ mol(-1) and -120 to -83 J K-1 mol(-1) ranges. Important intramolecular hydrogen bonding in the starting material can be held responsible for this difference with the remaining systems