Propofol exerts anti-inflammatory effects in rats with lipopolysaccharide-induced acute lung injury by inhibition of CD14 and TLR4 expression

We investigated the effect of propofol (Prop) administration (10 mg kg-1 h-1, intravenously) on lipopolysaccharide (LPS)-induced acute lung injury and its effect on cluster of differentiation (CD) 14 and Toll-like receptor (TLR) 4 expression in lung tissue of anesthetized, ventilated rats. Twenty-four male Wistar rats were randomly divided into three groups of 8 rats each: control, LPS, and LPS+Prop. Lung injury was assayed via blood gas analysis and lung histology, and tumor necrosis factor-α (TNF-α) and interleukin-1β (IL-1β) levels were determined in bronchoalveolar lavage fluid using ELISA. Real-time polymerase chain reaction was used to detect CD14 and TLR4 mRNA levels, and CD14 and TLR4 protein expression was determined by Western blot. The pathological scores were 1.2 ± 0.9, 3.3 ± 1.1, and 1.9 ± 1.0 for the control, LPS, and LPS+Prop groups, respectively, with statistically significant differences between control and LPS groups (P < 0.05) and between LPS and LPS+Prop groups (P < 0.05). The administration of LPS resulted in a significant increase in TNF-α and IL-1β levels, 7- and 3.5-fold, respectively (P < 0.05), while treatment with propofol partially blunted the secretion of both cytokines (P < 0.05). CD14 and TLR4 mRNA levels were increased in the LPS group (1.48 ± 0.05 and 1.26 ± 0.03, respectively) compared to the control group (1.00 ± 0.20 and 1.00 ± 0.02, respectively; P < 0.05), while propofol treatment blunted this effect (1.16 ± 0.05 and 1.12 ± 0.05, respectively; P < 0.05). Both CD14 and TLR4 protein levels were elevated in the LPS group compared to the control group (P < 0.05), while propofol treatment partially decreased the expression of CD14 and TLR4 protein versus LPS alone (P < 0.05). Our study indicates that propofol prevents lung injury, most likely by inhibition of CD14 and TLR4 expression.

SEPARATION OF SATURED AND UNSATURATED FATTY ACIDS FROM PALM FATTY ACIDS DISTILLATES IN CONTINUOUS MULTISTAGE COUNTERCURRENT COLUMNS WITH SUPERCRITICAL CARBON DIOXIDE AS SOLVENT: A PROCESS DESIGN METHODOLOGY

In this work the separation of multicomponent mixtures in counter-current columns with supercritical carbon dioxide has been investigated using a process design methodology. First the separation task must be defined, then phase equilibria experiments are carried out, and the data obtained are correlated with thermodynamic models or empirical functions. Mutual solubilities, Ki-values, and separation factors aij are determined. Based on this data possible operating conditions for further extraction experiments can be determined. Separation analysis using graphical methods are performed to optimize the process parameters. Hydrodynamic experiments are carried out to determine the flow capacity diagram. Extraction experiments in laboratory scale are planned and carried out in order to determine HETP values, to validate the simulation results, and to provide new materials for additional phase equilibria experiments, needed to determine the dependence of separation factors on concetration. Numerical simulation of the separation process and auxiliary systems is carried out to optimize the number of stages, solvent-to-feed ratio, product purity, yield, and energy consumption. Scale-up and cost analysis close the process design. The separation of palmitic acid and (oleic+linoleic) acids from PFAD-Palm Fatty Acids Distillates was used as a case study.

Continuous Counter-current Solvent Extraction of Magnesium and Calcium from Lithium-rich Brine

Solvent extraction of calcium and magnesium impurities from a lithium-rich brine (Ca ~ 2,000 ppm, Mg ~ 50 ppm, Li ~ 30,000 ppm) was investigated using a continuous counter-current solvent extraction mixer-settler set-up. The literature review includes a general review about resources, demands and production methods of Li followed by basics of solvent extraction. Experimental section includes batch experiments for investigation of pH isotherms of three extractants; D2EHPA, Versatic 10 and LIX 984 with concentrations of 0.52, 0.53 and 0.50 M in kerosene respectively. Based on pH isotherms LIX 984 showed no affinity for solvent extraction of Mg and Ca at pH ≤ 8 while D2EHPA and Versatic 10 were effective in extraction of Ca and Mg. Based on constructed pH isotherms, loading isotherms of D2EHPA (at pH 3.5 and 3.9) and Versatic 10 (at pH 7 and 8) were further investigated. Furthermore based on McCabe-Thiele method, two extraction stages and one stripping stage (using HCl acid with concentration of 2 M for Versatic 10 and 3 M for D2EHPA) was practiced in continuous runs. Merits of Versatic 10 in comparison to D2EHPA are higher selectivity for Ca and Mg, faster phase disengagement, no detrimental change in viscosity due to shear amount of metal extraction and lower acidity in stripping. On the other hand D2EHPA has less aqueous solubility and is capable of removing Mg and Ca simultaneously even at higher Ca loading (A/O in continuous runs > 1). In general, shorter residence time (~ 2 min), lower temperature (~23 °C), lower pH values (6.5-7.0 for Versatic 10 and 3.5-3.7 for D2EHPA) and a moderately low A/O value (< 1:1) would cause removal of 100% of Ca and nearly 100% of Mg while keeping Li loss less than 4%, much lower than the conventional precipitation in which 20% of Li is lost.

INVESTIGATIONS ON THE SOLVENT EXTRACTION AND LUMINESCENCE OF LANTHANOIDS WITH MIXTURES OF HETEROCYCLIC β- DIKETONE S AND VARIOUS NEUTRAL OXO-DONORS

The thesis entitled “ Investigations on the solvent extraction and luminescence of lanthanoids with mixtures of heterocyclic β-diketone S and various neutral oxo-donors” embodies the results of investigations carried out on the solvent extraction of trivalent lanthanoids with various heterocyclic β-diketones in the presence and absence of neutral oxo-donors and also on the luminescent studies of Eu3+-heterocyclic β-diketonate complexes with Lewis bases. The primary objective of the present work is to generate the knowledge base, especially to understand the interactions of lanthanoid-heterocyclic β-diketonates with various macrocyclic ligands such as crown ethers and neutral organophosphorus extractants , with a view to achieve better selectivity. The secondary objective of this thesis is to develop novel lanthanoid luminescent materials based on 3-phenyl-4-aroyl-5-isoxazolones and organophosphorus ligands, for use in electroluminescent devices. In the beginning it describes the need for the development of new mixed-ligand systems for the separation of lanthanoids and the development and importance of novel luminescent lanthanoid- β-diketonate complexes for display devices. The syntheses of various para substituted derivatives of 4-aroyl-5-isoxazolones and their characterization by various spectroscopic techniques are described. It also investigate the solvent extraction behaviour of trivalent lanthanoids with 4-aroyl-5-isoxazolones in the presence and absence of various crown ethers such as 18C6, DC18C6, DB18C6 and B18C6. Elemental analysis, IR and H NMR spectral studies are used to understand the interactions of crown ethers with 4-aroyl-5-isoxazolonate complexes of lanthanoids. The synergistic extraction of trivalent lanthanoids with sterically hindered 1-phenyl-3-methyl-4-pivaloyl-5-pyrazolone in the presence of various structurally related crown ethers are studied. The syntheses, characterization and photyphysical properties of Eu3+-4-aroyl-5-isoxazolonate complexes in the presence of Lewis bases like trictylphosphine oxide or triphenylphosphine oxide were studied.

Synergistic solvent extraction of Thorium(IV) and Uranium(VI) with β-diketones in presence of oxo-donors

The thesis entitled “Synergistic solvent extraction of Thorium(IV) and Uranium(VI) with β-diketones in presence of oxo-donors” embodies the results of the investigations carried out on the extraction of thorium(IV) an uranium(VI) with heterocyclic β-diketones in the presence and absence of various macrocyclic ligands and neutral organophosphorus extractants. The objective of this work is to generate the knowledge base to achieve better selectivity between thorium(IV) and uranium(VI) by understanding the interactions of crown ethers or neutral organophosphorus extractants with metal-heterocyclic β-diketonate complexes. Para-substituted 1-phenyl-3-methyl-4-aroyl-5-pyrazolones, namely,1-phenyl-3-methyl-4-(4-fluorobenzoyl)-5-pyrazolone (HPMFBP) and 1-phenyl-3-methyl-4-(4-toluoyl)-5-pyrazolone (HPMTP) were synthesized and characterized by elemental analysis, IR and H NMR spectral data. The synthesized ligands have been utilized for the extraction of thorium(IV) and uranium(VI) from nitric acid solutions in the presence and absence of various crown ethers. Thorium(IV) and uranium(VI) complexes with HPMPP(1-Phenyl-3-methyl-4-pivaloyl-5-pyrazolone) and neutral organophosphorus extractants were synthesized and characterized by IR and P NMR spectral data to further understand the interactions of neutral organophosphorus extractants with metal-chelates. Solid complexes of thorium(IV) and uranium(VI) with para-substituted 4-aroyl-5-isoxazolones and crown ethers were isolated and characterized by various spectroscopic techniques to further clarify the nature of the extracted complexes.

Studies on Photocatalysis by Nano Titania Modified with Non-Metals

The present work aims to prepare visible light responsive anion doped titania via sol-gel precipitation method.The prepared catalysts were characterized by various techniques.The photocatalytic abilities of the prepared catalysts were measured by the degradation of dyes,pesticides,hydrogen production through water splitting reaction and antibacterial study.We also compared the activities of prepared catalysts with pure titania prepared in the laboratory and one of the commercial anatase titania samples.

Studies on the Solvent Dependence in the Reaction of a Few (Anthracen-9-yl)MethyLamines and Sulfanes with Reactive Acetylenes

The thesis entitled ‘Studies on the Solvent Dependence in the Reaction of a Few (Anthracen-9-yl)methylamines and Sulfanes with Reactive Acetylenes’ is divided into six chapters. ln Chapter l a general survey of electron transfer reactions, Diels-Alder reactions and Michael-type additions is presented. A detailed discussion on the synthesis of several (anthracen-9-yl)methylamines is presented in Chapter 2. In Chapter 3, results of preliminary photophysical studies on a few (anthracen-9yl) methylamines are compiled. A detailed discussion on extensive examination of dependence in the reaction of (anthracen-9-yl)methylamines with reactive acetylenes is presented Chapter 4. Details on the synthesis and reaction of a few (anthracen-9-yl)methylsulfanes with DMAD are described in Chapter 5.

Information and anti-terrorist security of Poland. A critical analysis exemplified with the tasks and activity of the Internal Security Agency

The subject matter of the analysis conducted in the text is information and anti-terrorist security of Poland, which has been presented within the context of a clash between two spheres – the state and the private sphere. Furthermore, the issues of security have been supplemented with a description of the tasks and activity of the Internal Security Agency, as well as a synthetic appraisal of a terrorist threat to Poland. The main parts of this work are concerned with: (1) the state and the private sphere, (2) " terrorism " and terrorist offences, (3) the tasks and activity of the Internal Security Agency, (4) an appraisal of a terrorist threat to Poland. Given the necessity to elaborate the research problem, the text features the following research questions: (1) To what extent does referring to a threat to security influence a limitation on rights and freedoms in Poland (with regard to the clash between the state and the private sphere)?, (2) To what extent do the tasks and activity of the Internal Security Agency influence the effectiveness of anti-terrorist security in Poland?

Thioquinolobactin, a pseudomonas siderophore with antifungal and anti-pythium activity

Under conditions of iron limitation Pseudomonas fluorescens ATCC 17400 produces two siderophores, pyoverdine, and a second siderophore quinolobactin, which itself results from the hydrolysis of the unstable molecule 8-hydroxy-4-methoxy-2-quinoline thiocarboxylic acid (thioquinolobactin). Pseudomonas fluorescens ATCC 17400 also displays a strong in vitro antagonism against the Oomycete Pythium, which is repressed by iron, suggesting the involvement of a siderophore(s). While a pyoverdine-negative mutant retains most of its antagonism, a thioquinolobactin-negative mutant only slowed-down Pythium growth, and a double pyoverdine-, thioquinolobactin-negative mutant, which does not produce any siderophore, totally lost its antagonism against Pythium. The siderophore thioquinolobactin could be purified and identified from spent medium and showed anti-Pythium activity, but it was quickly hydrolysed to quinolobactin, which we showed has no antimicrobial activity. Analysis of antagonism-affected transposon mutants revealed that genes involved in haem biosynthesis and sulfur assimilation are important for the production of thioquinolobactin and the expression of antagonism.

Solvent extraction and lanthanide complexation studies with new terdentate ligands containing two 1,3,5-triazine moieties

The extracting agent 2,6-bis(4,6-di-pivaloylamino-1,3,5-triazin-2-yl)-pyridine (L-5) in n-octanol was found, in synergy with 2-bromodecanoic acid, to give D-Am/D-Eu separation factors (SFs) between 2.4 and 3.7 when used to extract the metal ions from 0.02-0.12 M HNO3. Slightly higher SFs (4-6) were obtained in the absence of the synergist when the ligand was used to extract Am(III) and Eu(III) from 0.98 M HNO3. In order to investigate the possible nature of the extracted species crystal structures of L-5 and the complex formed between Yb(III) with 2,6-bis(4,6-di-amino-1,3,5-triazin-2-yl)-pyridine (L-4) were also determined. The structure of L-5 shows 3 methanol solvent molecules all of which form 2 or 3 hydrogen bonds with triazine nitrogen atoms, amide nitrogen or oxygen atoms, or pyridine nitrogen atoms. However, L-5 is relatively unstable in metal complexation reactions and loses amide groups to form the parent tetramine L-4. The crystal structure of Yb(L-4)(NO3)(3) shows ytterbium in a 9-coordinate environment being bonded to three donor atoms of the ligand and three bidentate nitrate ions. The solvent extraction properties of L-4 and L-5 are far inferior to those found for the 2,6-bis-(1,2,4-triazin-3-yl)-pyridines (L-1) which have SF values of ca. 140 and theoretical calculations have been made to compare the electronic properties of the ligands. The electronic charge distribution in L-4 and L-5 is similar to that found in other terdentate ligands such as terpyridine which have equally poor extraction properties and suggests that the unique properties of L-1 evolve from the presence of two adjacent nitrogen atoms in the triazine rings.

Solvent extraction of Am(III) and Eu(III) from nitrate solution using synergistic mixtures of n-tridentate heterocycles and chlorinated cobalt dicarbollide

The separation by solvent extraction of Am-241(III) from Eu-152(III), in 1 M NaNO3 weakly acidic (pH 4) aqueous solutions, into dilute (ca. 10(-2) M) solutions of triazinylbipyridine derivatives (diethylhemi-BTP or di(benzyloxyphenyl) hemi-BTP) and chlorinated cobalt dicarbollide (COSAN) in 1-octanol or nitrobenzene has been studied. The N-tridentate heterocyclic ligands, which are selective for Am(III) over Eu(III), secured efficient separation of the two metal ions, while COSAN, strongly hydrophobic and fully dissociated in polar diluents, enhanced the extraction of the metal ions by ion-pair formation. Molecular interactions between the two co-extractants, observed at higher concentrations, led to the precipitation of their 1: 1 molecular adduct. In spite of that, efficient separations of Am and Eu ions were attained, with high separation factors, SFAm/Eu of 40 and even 60, provided the concentration of hemi-BTP was significantly greater than that of COSAN. Excess COSAN concentrations caused an antagonistic effect, decreasing both the distribution ratio of the metal ions and their separation factor.

Anti-tumor activity of Titanocene Y in xenografted Caki-1 tumors in mice

The benzyl-substituted unbridged titanocene bis-[(p-methoxybenzyl)cyclopentadienyl] titanium(IV) dichloride (Titanocene Y) was tested in vitro against human renal cancer cells (Caki-1), in which it showed an IC50 value of 36 x 10(-6) mol/l. Titanocene Y was then given in vivo in doses of 10, 20, 30, 40 and 50 mg/kg on 5 consecutive days to Caki-1-bearing mice, and it showed concentration-dependent and statistically significant tumor growth reduction with respect to a solvent-treated control cohort. The maximum tolerable dose of Titanocene Y was determined to be 40 mg/kg and it showed significantly better tumor volume growth reduction than cisplatin given at a dose of 2 mg/kg. This superior activity of Titanocene Y with respect to cisplatin will hopefully lead to clinical tests against metastatic renal cell cancer in the near future.

Ensemble prediction for nowcasting with a convection-permitting model—I: description of the system and the impact of radar-derived surface precipitation rates

A key strategy to improve the skill of quantitative predictions of precipitation, as well as hazardous weather such as severe thunderstorms and flash floods is to exploit the use of observations of convective activity (e.g. from radar). In this paper, a convection-permitting ensemble prediction system (EPS) aimed at addressing the problems of forecasting localized weather events with relatively short predictability time scale and based on a 1.5 km grid-length version of the Met Office Unified Model is presented. Particular attention is given to the impact of using predicted observations of radar-derived precipitation intensity in the ensemble transform Kalman filter (ETKF) used within the EPS. Our initial results based on the use of a 24-member ensemble of forecasts for two summer case studies show that the convective-scale EPS produces fairly reliable forecasts of temperature, horizontal winds and relative humidity at 1 h lead time, as evident from the inspection of rank histograms. On the other hand, the rank histograms seem also to show that the EPS generates too much spread for forecasts of (i) surface pressure and (ii) surface precipitation intensity. These may indicate that for (i) the value of surface pressure observation error standard deviation used to generate surface pressure rank histograms is too large and for (ii) may be the result of non-Gaussian precipitation observation errors. However, further investigations are needed to better understand these findings. Finally, the inclusion of predicted observations of precipitation from radar in the 24-member EPS considered in this paper does not seem to improve the 1-h lead time forecast skill.

The last glacial cycle: transient simulations with an AOGCM

A number of transient climate runs simulating the last 120kyr have been carried out using FAMOUS, a fast atmosphere-ocean general circulation model (AOGCM). This is the first time such experiments have been done with a full AOGCM, providing a three-dimensional simulation of both atmosphere and ocean over this period. Our simulation thus includes internally generated temporal variability over periods from days to millennia, and physical, detailed representations of important processes such as clouds and precipitation. Although the model is fast, computational restrictions mean that the rate of change of the forcings has been increased by a factor of 10, making each experiment 12kyr long. Atmospheric greenhouse gases (GHGs), northern hemisphere ice sheets and variations in solar radiation arising from changes in the Earth's orbit are treated as forcing factors, and are applied either separately or combined in different experiments. The long-term temperature changes on Antarctica match well with reconstructions derived from ice-core data, as does variability on timescales longer than 10 kyr. Last Glacial Maximum (LGM) cooling on Greenland is reasonably well simulated, although our simulations, which lack ice-sheet meltwater forcing, do not reproduce the abrupt, millennial scale climate shifts seen in northern hemisphere climate proxies or their slower southern hemisphere counterparts. The spatial pattern of sea surface cooling at the LGM matches proxy reconstructions reasonably well. There is significant anti-correlated variability in the strengths of the Atlantic Meridional Overturning Circulation (AMOC) and the Antarctic Circumpolar Current (ACC) on timescales greater than 10kyr in our experiments. We find that GHG forcing weakens the AMOC and strengthens the ACC, whilst the presence of northern hemisphere ice-sheets strengthens the AMOC and weakens the ACC. The structure of the AMOC at the LGM is found to be sensitive to the details of the ice-sheet reconstruction used. The precessional component of the orbital forcing induces ~20kyr oscillations in the AMOC and ACC, whose amplitude is mediated by changes in the eccentricity of the Earth's orbit. These forcing influences combine, to first order, in a linear fashion to produce the mean climate and ocean variability seen in the run with all forcings.

Secular trends in daily precipitation characteristics: greenhouse gas simulation with a coupled AOGCM

Secular trends of daily precipitation characteristics are considered in the transient climate change experiment with a coupled atmosphere-ocean general circulation model ECHAM4/OPYC3 for 1900-2099. The climate forcing is due to increasing concentrations of the greenhouse gases in the atmosphere. Mean daily precipitation, precipitation intensity, probability of wet days and parameters of the gamma distribution are analyzed. Particular attention is paid to the changes of heavy precipitation, Analysis of the annual mean precipitation trends for 1900-1999 revealed general agreement with observations with significant positive trends in mean precipitation over continental areas. In the 2000-2099 period precipitation trend patterns followed the tendency obtained for 1900-1999 but with significantly increased magnitudes. Unlike the annual mean precipitation trends for which negative values were found for some continental areas, the mean precipitation intensity and scale parameter of the fitted gamma distribution increased over all land territories . Negative trends in the number of wet days were found over most of the land areas except high latitudes in the Northern Hemisphere. The shape parameter of the gamma distribution in general revealed a slight negative trend in the areas of the precipitation increase. Investigation of daily precipitation revealed an unproportional increase of heavy precipitation events for the land areas including local maxima in Europe and the eastern United States.