Rapid synthesis of nucleotide pyrophosphate linkages in a ball mill

Using a ball mill, rapid, atom-economic coupling between adenosine-5'-phosphoromorpholidate and phosphorylated ribose derivatives as their sodium or barium salts was achieved. Facile purification by reversed-phase HPLC enabled product isolation within hours.

Synthesis of caffeic acid and p-hydroxybenzoic acid molecularly imprinted polymers and their application for the selective extraction of polyphenols from olive mill waste waters

Using caffeic acid and p-hydroxybenzoic acid as templates, two molecularly imprinted polymers (MIPs) were prepared that were used for isolation of polyphenols from olive mill waste water samples (OMWWs) without previous pre-treatment. For the preparation of the caffeic acid MIPs 4-vinylpyridine, allylurea, allylaniline and methacrylic acid were tested as functional monomers, ethylene glycol dimethylacrylate (EDMA), pentaerythritol trimethylacrylate (PETRA) and divinylbenzene 80 (DVB80) as cross-linkers and tetrahydrofuran as porogen. For p-hydroxybenzoic acid 4-vinylpyridine, allylurea and allylaniline were tested as functional monomers, EDMA and PETRA as cross-linkers and acetonitrile as porogen. The performance of the synthesized polymers was evaluated against seven structurally related compounds by means of polymer-based HPLC. The two polymers that presented the most interesting properties were further evaluated by batch rebinding and from the derived isotherms their capacity and binding strength were determined. Using solid-phase extraction (SPE), their ability to recognize and bind the template molecule from an aqueous solution as well as the pH dependence of the binding strength were explored. After establishing the best SPE protocol, an aqueous model mixture of compounds and a raw OMWWs sample were loaded on the two best polymers. The result of the consecutive use of the two polymers on the same sample was explored. It was concluded that acidic conditions favour the recognition abilities of both polymers and that they can be used for a quick and efficient isolation of the polyphenol fraction directly from raw OMWW.

Clarification of rubber mill wastewater by a plant based biopolymer- comparison with common inorganic coagulants

Background: In this study, the efficiency of Guar gum as a biopolymer has been compared with two other widely used inorganic coagulants, ferric chloride (FeCl3) and aluminum chloride (AlCl3), for the treatment of effluent collected from the rubber-washing tanks of a rubber concentrate factory. Settling velocity distribution curves were plotted to demonstrate the flocculating effect of FeCl3, AlCl3 and Guar gum. FeCl3 and AlCl3 displayed better turbidity removal than Guar gum at all settling velocities.

Result: FeCl3, AlCl3 and Guar gum removed 92.8%, 88.2% and 88.1% turbidity, respectively, of raw wastewater at a settling velocity of 0.1 cm min-1, respectively. Scanning electron microscopic (SEM) study conducted on the flocs revealed that Guar gum and FeCl3produced strong intercoiled honeycomb patterned floc structure capable of entrapping suspended particulate matter. Statistical experimental design Response Surface Methodology (RSM) was used to design all experiments, where the type and dosage of flocculant, pH and mixing speed were taken as control factors and, an optimum operational setting was proposed.

Conclusion: Due to biodegradability issues, the use of Guar gum as a flocculating agent for wastewater treatment in industry is highly recommended.

Field observation of sequestration of uranium in iron-rich sediments under sequential reduction-oxidation conditions at the DOE Oak Ridge IFRC

At the U.S. DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site, the iron content of shallow subsurface materials (i.e. weathered saprolite) is relatively high (up to 5-6% as w/w), and therefore, the forms of the iron species present plays a critical role in the long-term sequestration of uranium. A long term pilot-scale study of the bioreduction and reoxidation of uranium conducted at the ORIFRC area 3 site, adjacent to the former S-3 disposal ponds (source zone), has provided us with the opportunity to study the impact of iron species on the sequestration of U(VI). The aqueous U(VI) concentrations at the site were decreased to below the EPA MCL through the intermittent injection of ethanol as the electron donor. Previous field tests indicated that both oxygen and nitrate could oxidize the bioreduced U(IV) and cause a short-term rebound of aqueous phase uranium concentration after the oxidative agents were delivered directly to the bioreduced zone.

A field test has been conducted to examine the long-term effect of exposure of bioreduced sediments to nitrate in contaminated groundwater for more than 1,380 days at the Area 3 site. Contaminated groundwater was allowed to invade the previously bioreduced zone via the natural groundwater gradient after an extended period in which reducing conditions were maintained and the bioreduced zone was protected from the influx of upgradient contaminated groundwater. The geochemical response to the invasion of contaminated groundwater was dependent on whether the monitoring location is in the middle or the fringe of the previously bioreduced zone. In general, the nitrate concentrations in the previously bioreduced area, increased gradually from near zero to ~50-300 mM within 200 days and then stabilized. The pH declined from bioreduced levels of 6.2-6.7 to below 5.0. Uranium concentrations rebounded in all monitoring wells but at different rates. At most locations U concentrations rebounded, declined and then rebounded again. Methane gas disappeared while a significant level (20,000 to 44,000 ppmv) N2O was found in the groundwater of monitoring wells after three years of reoxidization.

The U(IV) in sediments was mainly reoxidized to U(VI) species. Based on XANES analysis, the predominate uranium in all samples after re-oxidation was similar to a uranyl nitrate form. But the U content in the sediment remained as high as that determined after bioreduction activates were completed, indicating that much of the U is still sequestrated in situ. SEM observations of surged fine sediments revealed that clusters of colloidal-sized (200-500nm) U-containing precipitates appeared to have formed in situ, regardless from sample of FW106 in non-bioactivity control area or of pre-bioreduced FW101-2 and FW102-3. Additionally, SEM-EDS and microprobe analysis, showed that the U-containing precipitates (~1% U) in FW106 are notably higher in Fe, compared to the precipitates (~1-2.5% U) from FW101-2 and FW102-3. However, XRF analysis indicated that the U content was remained as high as 2180 and 1810 mg/kg with U/Fe ratio at 0.077 and 0.055 vs 0.037 g/g, respectively in pre-bioreduced FW101-2 and FW102-3, suggesting more U sequestrated by Fe in pre-bioreduced sediments.

A comparative study of biopolymers and alum in the separation and recovery of pulp fibres from paper mill effluent by flocculation

Recovery of cellulose fibres from paper mill effluent has been studied using common polysaccharides or biopolymers such as Guar gum, Xanthan gum and Locust bean gum as flocculent. Guar gum is commonly used in sizing paper and routinely used in paper making. The results have been compared with the performance of alum, which is a common coagulant and a key ingredient of the paper industry. Guar gum recovered about 3.86 mg/L of fibre and was most effective among the biopolymers. Settling velocity distribution curves demonstrated that Guar gum was able to settle the fibres faster than the other biopolymers; however, alum displayed the highest particle removal rate than all the biopolymers at any of the settling velocities. Alum, Guar gum, Xanthan gum and Locust bean gum removed 97.46%, 94.68%, 92.39% and 92.46% turbidity of raw effluent at a settling velocity of 0.5 cm/min, respectively. The conditions for obtaining the lowest sludge volume index such as pH, dose and mixing speed were optimised for guar gum which was the most effective among the biopolymers. Response surface methodology was used to design all experiments, and an optimum operational setting was proposed. The test results indicate similar performance of alum and Guar gum in terms of floc settling velocities and sludge volume index. Since Guar gum is a plant derived natural substance, it is environmentally benign and offers a green treatment option to the paper mills for pulp recycling.

Uranium halide complexes in ionic liquids: an electrochemical and structural study

The electrochemistry of the salts, [emim](2)[UBr6] and [emim](2)[UO2Br4] ([emim] = 1-ethyl-3-methylimidazolium), has been investigated in both a basic and an acidic bromoaluminate(III) ionic liquid. In the basic ionic liquid, the hexabromo salt undergoes a one-electron reversible reduction process at a stationary glassy carbon disc electrode, while the tetrabromodioxo salt was reduced to a uranium(IV) species by an irreversible two-electron process with the simultaneous transfer of oxide to the ionic liquid. On the other hand, dissolution of either of the salts in an acidic bromoaluminate( III) ionic liquid resulted in the formation of the same electroactive species. The solid state structures of the uranium chloride salts, [emim](2)[UCl6] and [emim](2)[UO2Cl4], have previously been reported, but have now been re-evaluated using a new statistical model developed in our group, to determine the presence or absence of weak hydrogen bonding interactions in the crystalline state.

Dissolved uranium, radium and radon evolution in the Continental Intercalaire aquifer, Algeria and Tunisia

Natural, dissolved 238U-series radionuclides (U, 226Ra, 222Rn) and activity ratios (A.R.s: 234U/238U; 228Ra/226Ra) in Continental Intercalaire (CI) groundwaters and limited samples from the overlying Complexe Terminal (CT) aquifers of Algeria and Tunisia are discussed alongside core measurements for U/Th (and K) in the contexts of radiological water quality, geochemical controls in the aquifer, and water residence times. A redox barrier is characterised downgradient in the Algerian CI for which a trend of increasing 234U/238U A.R.s with decreasing U-contents due to recoil-dominated 234U solution under reducing conditions allows residence time modelling ∼500 ka for the highest enhanced A.R. = 3.17. Geochemical modelling therefore identifies waters towards the centre of the Grand Erg Oriental basin as palaeowaters in line with reported 14C and 36Cl ages. A similar 234U/238U trend is evidenced in a few of the Tunisian CI waters. The paleoage status of these waters is affirmed by both noble gas recharge temperatures and simple modelling of dissolved, radiogenic 4He-contents both for sampled Algerian and Tunisian CI and CT waters. For the regions studied these waters therefore should be regarded as “fossil” waters and treated effectively as a non-renewable resource.

Distribution of Uranium and Thorium in Dolomitic Gravel Fill and Shale Saprolite

The objectives of this study were to examine (1) the distribution of U and Th in dolomitic gravel fill and shale saprolite, and (2) the removal of uranium from acidic groundwater by dolomitic gravel through precipitation with amorphous basaluminite at the U.S. DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) field site west of the Oak Ridge Y-12 National Security Complex in East Tennessee. Media reactivity and sustainability are a technical concern with the deployment of any subsurface reactive media. Because the gravel was placed in the subsurface and exposed to contaminated groundwater for over 20 years, it provided a unique opportunity to study the solid and water phase geochemical conditions within the media after this length of exposure. This study illustrates that dolomite gravel can remove U from acidic contaminated groundwater with high levels of Al3+, Ca2+, NO3−, and SO42− over the long term. As the groundwater flows through high pH carbonate gravel, U containing amorphous basaluminite precipitates as the pH increases. This is due to an increase in groundwater pH from 3.2 to ∼6.5 as it comes in contact with the gravel. Therefore, carbonate gravel could be considered as a possible treatment medium for removal and sequestration of U and other pH sensitive metals from acidic contaminated groundwater. Thorium concentrations are also high in the carbonate gravel. Thorium generally shows an inverse relationship with U from the surface down into the deeper saprolite. Barite precipitated in the shallow saprolite directly below the dolomitic gravel from barium present in the acidic contaminated groundwater.

Nucleoside Azide-Alkyne Cycloaddition Reactions Under Solvothermal Conditions or Using Copper Vials in a Ball Mill

Novel nucleoside analogues containing photoswitchable moieties were prepared using 'click' cycloaddition reactions between 5 '-azido-5 '-deoxythymidine and mono- or bis-N-propargylamide-substituted azobenzenes. In solution, high to quantitative yields were achieved using 5mol% Cu(I) in the presence of a stabilizing ligand. 'Click' reactions using the monopropargylamides were also effected in the absence of added cuprous salts by the application of liquid assisted grinding (LAG) in metallic copper reaction vials. Specifically, high speed vibration ball milling (HSVBM) using a 3/32('') (2.38mm) diameter copper ball (62mg) at 60Hz overnight in the presence of ethyl acetate lead to complete consumption of the 5 '-azido nucleoside with clean conversion to the corresponding 1,3-triazole.

Numerical analysis of impact events in a centrifugal impact pin mill

Milling is an important operation in many industries, such as mining and pharmaceutical. Although the comminution process during milling has been extensively studied, the material fragmentation mechanisms in a mill are still not well understood partly because of the lack of an understanding on the local stressing and dynamic information under operational conditions in mills. This paper presents a DEM simulation of particle dynamics and impact events in a centrifugal impact pin mill. The main focus is the statistical characteristics of the dominant stressing modes during the milling process. The frequency, velocity and force of the different impact events between particles and mill components, or between particles, are analysed. © 2013 AIP Publishing LLC.

2P/Encke, the Taurid complex NEOs and the Maribo and Sutter's Mill meteorites

Aims. 2P/Encke is a short period comet that was discovered in 1786 and has been extensively observed and studied for more than 200years. The Taurid meteoroid stream has long been linked with 2P/Encke owing to a good match of their orbital elements, even thoughthe comet’s activity is not strong enough to explain the number of observed meteors. Various small near-Earth objects (NEOs) havebeen discovered with orbits that can be linked to 2P/Encke and the Taurid meteoroid stream. Maribo and Sutter’s Mill are CM typecarbonaceous chondrite that fell in Denmark on January 17, 2009 and April 22, 2012, respectively. Their pre-atmospheric orbits placethem in the middle of the Taurid meteoroid stream, which raises the intriguing possibility that comet 2P/Encke could be the parentbody of CM chondrites.
Methods. To investigate whether a relationship between comet 2P/Encke, the Taurid complex associated NEOs, and CM chondritesexists, we performed photometric and spectroscopic studies of these objects in the visible wavelength range. We observed 2P/Enckeand 10 NEOs on August 2, 2011 with the FORS instrument at the 8.2 m Very Large Telescope on Cerro Paranal (Chile).
Results. Images in the R filter, used to investigate the possible presence of cometary activity around the nucleus of 2P/Encke andthe NEOs, show that no resolved coma is present. None of the FORS spectra show the 700 nm absorption feature due to hydratedminerals that is seen in the CM chondrite meteorites. All objects show featureless spectra with moderate reddening slopes at λ < 800nm. Apart for 2003 QC10 and 1999 VT25, which show a flatter spectrum, the spectral slope of the observed NEOs is compatible withthat of 2P/Encke. However, most of the NEOs show evidence of a silicate absorption in lower S/N data at λ > 800 nm, which is notseen in 2P/Encke, which suggests that they are not related.
Conclusions. Despite similar orbits, we find no spectroscopic evidence for a link between 2P/Encke, the Taurid complex NEOs andthe Maribo and Sutter’s Mill meteorites. However, we cannot rule out a connection to the meteorites either, as the spectral differencesmay be caused by secondary alteration of the surfaces of the NEOs. 

Synthesis of novel pyrophosphorothiolate-linked dinucleoside cap analogues in a ball mill

Michaelis–Arbuzov reactions of S-aryl disulfide derivatives of 3′-thiothymidine or 5′-thioadenosine with tris(trimethylsilyl) phosphite proceeded in high yields to the corresponding phosphorothiolate monoesters. Subsequent hydrolytic desilylation and phosphate coupling were effected in one-pot using liquid-assisted grinding in a vibration ball mill. Novel 3′,5′- and 5′,5′-pyrophosphorothiolate-linked dinucleoside cap analogues were thereby prepared.