A new way to perform reactions in core—shell double emulsions is reported herein. The phase boundaries of the threephase droplet flow were used to pressurize the reactants in the shell liquid, enhancing the reaction rate of a cycloaddition greatly in comparison to known methods. As key parameters, solvophobic effects and precise control over the droplet sizes were used to exploit a reaction with a negative volume of activation. The internal pressure of the reaction solution was regulated purely by the thickness of the shell liquid without adding additional reagents. Additionally, the reaction performed better when the core droplet was used to stir the shell droplet, considerably improving the mass transfer inside the otherwise diffusion-limited process.
Authors:K. Aleklett, R. Brandt, M. Bronikowski, V. Butsev, B. Chasteler, G. Dersch, G. Feige, E. Friedlander, E. Ganssauge, G. Haase, J. Herrmann, D. Hoffman, B. Judek, P. Kosma, B. Kulakov, E. Langrock, D. Lee, W. Loveland, F. Pille, N. Porile, W. Schulz, and G. Seaborg
In recent years the question of the unusual behavior of projectile fragments formed in the interaction of relativistic heavy ions with copper nuclei was studied using nuclear chemistry techniques. As targets we used various copper disk arrangements. It is not the intention of this conference contribution to give a complete account of the entire procedure and its results. However, we want to present a few more recent experimental findings, some of them even in a preliminary form. We want to stimulate the discussion about the entire problem which might be part of the so-called anomalon phenomenon, as observed in the field of relativistic heavy ion interactions with a few other techniques such as nuclear emulsions or bubble chambers.
Authors:Guo Jin-xin, Sun Si-xiu, Zhu Rong-xiu, Yin Zhi-lei, Yu Hai-yun, Li Da-zhi, Zhang Wei-min, Xu Xian-gang, Sun Xuan, and Shao Hua
The mechanism of solvent extraction of uranium(VI) from highly concentrated chloride solution with a quaternary ammonium salt,
benzyloctadecyldimethylammonium chloride (BODMAC, R4NCl), dissolved in chloroform was studied. The compositions of the extracted species were R4N.UO2Cl3 and (R4N)2.UO2Cl4. The extraction process is exothermic (ΔH° = -8.42±0.54 KJ/mol). Kex1 and Kex2 are calculated to be (3.62±0.55).10-2 and (1.06±0.17).103, respectively. In the extraction process, a W/O uranium(VI) rich emulsion solution has been formed between the organic and
aqueous phases, its volume increased with the increase of BODMAC in the system. The influences of temperature, NaCl, MgCl2 and MgSO4 concentrations on the extraction equilibrium were also studied.
A calorimetric investigation was performed on the partition ofn-pentanol in the external oil phase and in the interfacial layer of the water-in-oil microemulsion system sodium dodecyl-benzenesulfonate(DDBS)/n-pentanol/n-heptane/water. The results show that fine changes can be observed in the structure of the water-in-oil emulsion and microemulsion
droplets, such as then-pentanol/DDBS mole ratio increase in the interfacial layer; further, the alcohol/surfactant mole ratio α in the interfacial
layer of the droplets, and also the standard thermodynamic functions of the alcohol transition from the external phase to
the interfacial phase (ΔGe→so
), can be derived from calorimetric data.
Authors:Baki Sadi, Chunsheng Li, Gary Kramer, Cassandra Johnson, Queenie Ko, and Edward Lai
A new radioanalytical method was developed for rapid determination of 226Ra in drinking water samples. The method is based on extraction and preconcentration of 226Ra from a water sample to an organic solvent using a dispersive liquid-liquid microextraction (DLLME) technique followed by
radiometric measurement using liquid scintillation counting. In DLLME for 226Ra, a mixture of an organic extractant (toluene doped with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone) and a disperser
solvent (acetonitrile) is rapidly injected into the water sample resulting in the formation of an emulsion. Within the emulsion,
226Ra reacts with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone and partitions into the fine droplets of toluene. The water/toluene
phases were separated by addition of acetonitrile as a de-emulsifier solvent. The toluene phase containing 226Ra was then measured by liquid scintillation counting. Several parameters were studied to optimize the extraction efficiency
of 226Ra, including water immiscible organic solvent, disperser and de-emulsifier solvent type and their volume, chelating ligands
for 226Ra and their concentrations, inorganic salt additive and its concentration, and equilibrium pH. With the optimized DLLME conditions,
the accuracy (expressed as relative bias, Br) and method repeatability (expressed as relative precision, SB) were determined by spiking 226Ra at the maximum acceptable concentration level (0.5 Bq L−1) according to the Guidelines for Canadian Drinking Water Quality. Accuracy and repeatability were found to be less than −5%
(Br) and less than 6% (SB), respectively, for both tap water and bottled natural spring water samples. The minimum detectable activity and sample turnaround
time for determination of 226Ra was 33 mBq L−1 and less than 3 h, respectively. The DLLME technique is selective for extraction of 226Ra from its decay progenies.
Authors:Mirta Balenović, Vladimir Savić, Anamaria Ekert Kabalin, Luka Jurinović, and William Ragland
As immune responses to live and inactivated vaccines might differ, temporal responses of broiler chickens to vaccination were examined on the basis of the abundance in the circulating blood of gene transcripts of IFN-α, IFN-γ and IL-2, critical cytokines for immune responses. Blood samples were collected 6, 12 and 24 hours, and 7 and 14 days following vaccination with either live or inactivated Newcastle disease virus, La Sota strain, at 14 days of age, and the abundance of transcripts for each cytokine was assayed by real-time RT-PCR. Physiological saline and vaccine emulsion without viral antigen were administered to control groups for live and inactivated vaccine groups, respectively. The abundance of IFN-γ transcripts was elevated during the early times following vaccination and had reached baseline by the seventh day but the abundance of IFN-α transcripts remained elevated. Transcripts for neither IFN gene were detected in the control birds. The abundance of transcripts for each IFN was not different between the two vaccinated groups at any time. Transcripts for IL-2 were detected only in spleens from chicken embryos that had been inoculated with the live virus. The results show that cells stimulated to produce IFN-α and IFN-γ enter the circulating blood but those stimulated to produce IL-2 do not, or in very low number, and the IFN responses to both vaccines are the same.
C-reactive protein (CRP) and haptoglobin (Hp) are well-known acute phase proteins in the dog. Currently, a commercial ELISA and a colorimetric assay are the methods of choice for measuring CRP and Hp, respectively; however, these assays showed interference when using haemolysed, lipaemic or hyperbilirubinaemic samples. Recently, time-resolved immunofluorometric assays (TRIFMAs) have been developed for measuring canine CRP and Hp. The aim of the present study was to evaluate the effect of increasing concentrations of haemoglobin, lipids and bilirubin in CRP and Hp serum measurements using these new fluoroimmunoassays. Haemolysis was produced by freezing blood cells at −20°C. The haemolysate was added to pooled sera at final concentrations of 0, 2.5, 5, 10, 20 and 40 g/L. A commercial emulsion of triglycerides was added to homologous pooled sera at 0, 0.35, 0.7, 1.4, 2.8, 5.6 and 11.2 mmol/L. Bilirubin, initially dissolved in dimethyl sulphoxide, was added to pooled sera at 0, 64.2, 128.4, 256.8, 513.7 and 1027.4 μmol/L. Addition of fresh haemolysate, triglycerides or bilirubin to serum samples did not affect either CRP or Hp concentrations (P ≥ 0.18), so the TR-IFMAs could be an alternative to the traditional tests for measuring canine CRP and Hp in those laboratories where immunofluorometric assays are available.
Authors:Ali Mohammad, Vineeta Agrawal, and Sanjeev Kumar
A water-in-oil microemulsion has been used for the first time as a mobile phase in thin-layer chromatography of amino acids. A new TLC system comprising silica gel layers impregnated with micellar copper sulfate solution as stationary phase and a water-in-oil microemulsion as mobile phase has been proposed for selective separation of DL
-phenylalanine from other amino acids. Experimental conditions have been optimized and TLC conditions for separation of DL
-phenylalanine in the presence of foreign impurities were determined. Improved separation of amino acids, but with reduced sensitivity, was realized on silica gel layers impregnated with metal ions such as Li
, and Th
. Silica gel impregnated with a 1:1 mixture of 2% aqueous CuSO
and 3% Brij-35 was found to be the best layer material for rapid separation of amino acids (development time 10 min) using a water-in-oil microemulsion as mobile phase. The water content of the emulsion had little effect on the mobility of the amino acids.
The crystallisation properties of a mixture of triacylglycerols (TG), cocoa butter (CB) 75%/miglyol 25%, were investigated
on cooling at 0.5 °C/min using differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The influence of (i) the
dispersion of TG within nanoparticles stabilised by proteins, and of (ii) the presence of polar lipids were characterised.
In bulk, crystallisation of TG successively occurred with a α 2L (49.3 Å) structure, then the formation of longitudinal stackings
of 44.5 and 34.5 Å of β′ form was interpreted as co-crystallisation of TG from CB and miglyol. The dispersion of TG in nanoparticles
of about 400 nm induced a higher supercooling and changed their crystallisation properties. The formation of α 49.2 Å and
β′ 45 Å structures corresponded to the segregation of TG from CB in solid phases while TG from miglyol remained liquid. Phospholipids
with saturated fatty acid chains affected the thermal properties of TG, which demonstrated their localisation at the surface
of the nanoparticles. DSC and XRD revealed to be very sensitive and adapted methods to increase the knowledge about the mechanisms
of crystallisation in emulsion.
Ammonium dinitramide (ADN) prills were prepared by emulsion crystallization and characterized by optical microscopic, thermogravimetric
(TG) and differential scanning calorimetric (DSC) techniques. The isothermal and non-isothermal decomposition kinetics of
ADN prills were studied by TG. The differential isoconversional method of Friedman (FR) and integral isoconversional method
of Vyazovkin were used to investigate the dependence of activation energy (Ea) with conversion (α) and the results were compared with literature data. The dependence of activation energy was also derived
from isothermal data. A strong dependence of Ea with α is observed for the ADN prills. All the methods showed an initial increase in Ea up to α=∼0.2 and later decreases over the rest of conversion. The apparent Ea values of FR method are higher than that of Vyazovkin method up to α=∼0.45. The calculated mean Ea values by FR, Vyazovkin and standard isoconversional method for α between 0.05 and 0.95 were 211.0, 203.9 and 156.9 kJ mol−1, respectively.