Water-soluble polymers for hostile environment enhanced oil recovery applications

This paper describes polymerization and properties of a number of water-soluble polymers suitable for enhanced oil recovery applications. The polymers described here can tolerate long-term exposure to hostile environment conditions of elevated temperatures and high salinity and hardness levels encountered in deeper petroleum reservoirs. The stable polymers reported here, in principle contain two or more of the following monomers: acrylamide, N-vinyl-2-pyrrolidone, sodium 2-acrylamido-2-methylpropanesulfonate and N,N-dimethylacrylamide in proper ratios. The polymers reported here can be used directly to increase the viscosity of the injected water and consequently reducing its mobility to recover additional oil from petroleum reservoirs. Alternatively, these polymers can be used in combination with a suitable crosslinker to produce gels in-situ to block high permeability channels or fractures under hostile environment applications.     

Water-soluble polymers for binding hydrophobic biologically active compounds

Russian Chemical Bulletin - Water-soluble neutral and charged copolymers of cholesterol methacrylate with 2-deoxy2-methacrylamido-D-glucose and methyl sulfate salt of N,N,N-trimethyl(aminoethyl...     

Optimisation of microdialysis sampling recovery by varying inner cannula geometry

In vitro microdialysis recoveries of glucose were evaluated and optimised by varying the inner cannula dimensions for a concentric type microdialysis probe. The recovery was shown to be significantly dependent on the outer radius of the inner cannula (r alpha). Increasing r alpha by 50% while holding all other microdialysis variables constant caused a 26% increase in recovery under the conditions tested. Mass transport modeling of microdialysis sampling showed that the magnitude of the recovery change in response to changes in r alpha may depend on other experimental variables such as effective dialysis length, membrane dimensions, membrane type and medium composition. These data indicate that microdialysis recovery may be substantially improved by optimising the outer diameter of the inner cannula. These data also suggest that in order to fully characterise and compare data from microdialysis experiments, r alpha should become one of the reported variables.     

No delayed temporal response to sample concentration changes during enhanced microdialysis sampling using cyclodextrins and antibody-immobilized microspheres

The temporal response to concentration changes external to a microdialysis probe containing trapping agents in the perfusion fluid was studied. Native beta-cyclodextrin and a water-soluble beta-cyclodextrin polymer were used as trapping agents in the microdialysis perfusion fluid to study the temporal concentration response to carbamazepine, a hydrophobic analyte. The temporal response of microdialysis probes containing antibody-immobilized microspheres against five different cytokines (tumor necrosis factor-alpha (TNF-alpha), interferon-gamma (IFN-gamma), interleukin-2 (IL-2), IL-4, and IL-5) to concentration changes outside of the probe was also determined. In both cases, no delayed temporal response of enhanced microdialysis was observed for either carbamazepine or the cytokines as compared to standard microdialysis sampling procedures.     

Enantioselective detection of chiral phosphorescent analytes in cyclodextrin complexes

Inclusion complexes between camphorquinone (CQ) and cyclodextrins (CDs) in deoxygenated aqueous solutions are shown to exhibit relatively strong room temperature phosphorescence (RTP). Among the various CDs tested, α-CD showed the strongest RTP signals. Interestingly, these signals differed significantly for the two enantiomers of CQ; the phosphorescence lifetime of (+)-CQ was about four times longer than that of (−)-CQ, being 352 ± 16 and 89 ± 6 μs, respectively. This enantiomeric selectivity is attributed to a difference in dissociation rates (competing with the radiative emission process) for the diastereoisomeric inclusion complexes dealt with, which have a 2:1 stoichiometry (α-CD:CQ:α-CD). Time-resolved RTP detection using different delay times enables the determination of the two enantiomers in a mixture without involving a separation technique. The minimum detectable fraction of (+)-CQ in a 2 mM sample was 13%.     

Enhancing the microdialysis recovery for sampling of Cu and Ni by incorporating humic acid in the perfusion liquid

A strategy to enhance the microdialysis relative recovery for sampling of Cu and Ni ions is presented. Enhanced recovery was achieved by incorporating humic acid, a binding agent, in the microdialysis perfusion liquid during sampling from a Cu and Ni standard solution mixture. All microdialysis sampling experiments were carried out at room temperature under quiescent conditions using a concentric type of microdialysis probe with an adjustable effective dialysis length. For all metal determinations electrothermal atomic absorption spectrometry was employed. Metal recoveries were shown to be dependent on the membrane molecular weight cut-off, perfusion rate, sample solution pH, perfusion liquid composition as well as perfusion liquid pH. Complete recoveries (100%) of Cu and Ni were obtained by microdialysis sampling using a 10 kDa molecular weight cut-off polysulfone membrane at a flow-rate of 2 μl/min employing a 0.05% (w/v) optimal composition of humic acid incorporated in the perfusion liquid. The optimal sampling pH of humic acid was determined to be 6 where most oxygen containing functional groups are dissociated and available for metal binding. These data have important ramifications for sampling and determination of metal ions in small sample solutions (∼10 ml) at very low concentrations in the ppb range.     

Effect of pumping methods on transmembrane pressure, fluid balance and relative recovery in microdialysis

There is a growing interest in using large pore size probes for microdialysis of macromolecular markers to monitor cell and tissue functions. Fluid balance could be an important issue when using large pore size microdialysis probes, which are affected by the mode of operation. In this study, the effect of pumping systems, push, pull, push-and-pull, and the resulting transmembrane pressure on the fluid balance, as well as, the relative recovery of small molecular nutrients and metabolites and macromolecules (proteins) were examined. The validity of the internal reference in situ calibration was examined in detail. It is concluded that a push-and-pull system is the only effective method of eliminating fluid loss or gain. The relative recovery of small solutes is not affected much by the applied pumping methods; however, the relative recovery of macromolecules is significantly influenced by them. The in situ calibration technique using Phenol Red can provide reliable results for small molecules including glucose and lactic acid. Using 10 and 70-kDa fluorescent dextrans as the internal standard for large molecules in situ calibration of similar size does not work for the pull pump system, but does work well when using a push-and-pull pumping method.     

Relaxation spectra of polymers and phenomena of electrical and hydrophobic recovery: Interplay between bulk and surface properties of polymers

Low‐density polyethylene, polypropylene, and polycarbonate were exposed to cold air plasma treatment. The decay of electret response, hydrophobic recovery, and mechanical relaxation of polymers were studied experimentally. The three‐exponential decay kinetic model was used for the treatment of mechanical and electret responses. The characteristic time scales of mechanical and electret responses turned out to be very close. The “longest” relaxation time, extracted from the experimental study of the hydrophobic recovery, was also close to the corresponding characteristic time spans of electret and mechanical responses. The kinetics of surface processes taking place in polymers is controlled by the mobility of their functional groups, represented by the bulk relaxation spectra. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 198–205     

Carbon nanotube immobilized polar membranes for enhanced extraction of polar analytes

We demonstrate for the first time that carbon nanotubes (CNTs) can be readily immobilized on the surface of a solid polymeric membrane which can lead to enhanced enrichment factor and extraction efficiency. The effectiveness of the CNT mediated process is demonstrated by micro-scale membrane extraction via direct solvent enrichment of polar and nonpolar organics. The enrichment factor measured as the ratio of concentrations in the acceptor to the donor phases was as high as 282 and the enhancement over the unmodified membrane was as much as 92%. In addition, the solvent retention in the carbon nanotube immobilized membrane (CNIM) increased by as much as 29%. Overall, the CNT incorporation provided enhanced solute transport and thus led to overall performance enhancement.     

Water-soluble dendritic core-shell-type architectures based on polyglycerol for solubilization of hydrophobic drugs

Since many potential drugs are poorly water soluble, there is a high demand for solubilization agents. Here, we describe the synthesis of dendritic core-shell-type architectures based on hyperbranched polyglycerol for the solubilization of hydrophobic drugs. Amphiphilic macromolecules containing hydrophobic biphenyl groups in the core were synthesized in an efficient three- or four-step procedure by employing Suzuki-coupling reactions. These species were then used to solubilize the commercial drug nimodipine, a calcium antagonist used for the treatment of heart diseases and neurological deficits. Pyrene was also used as a hydrophobic model compound. It turned out that the transport properties of the dendritic polyglycerol derivatives, which are based on hydrophobic host-guest interactions, depend strongly on the degree and type of core functionalization. In the case of the multifunctional nimodipine, additional specific polymer-drug interactions could be tailored by this flexible core design, as detected by UV spectroscopy. The enhancement of solubilization increased 300-fold for nimodipine and 6000-fold for pyrene at a polymer concentration of 10 wt%. The sizes of the polymer-drug complexes were determined by both dynamic light scattering (DLS) experiments and transmission electron microscopy (TEM), and extremely well-defined aggregates with diameters of approximately 10 nm in the presence of a drug were observed. These findings together with a low critical aggregate concentration of 4x10(-6) mol L-1 indicate the controlled self-assembly of the presented amphiphilic dendritic core-shell-type architectures rather than a unimolecular transport behavior.     

An integrate-over-temperature approach for enhanced sampling

A simple method is introduced to achieve efficient random walking in the energy space in molecular dynamics simulations which thus enhances the sampling over a large energy range. The approach is closely related to multicanonical and replica exchange simulation methods in that it allows configurations of the system to be sampled in a wide energy range by making use of Boltzmann distribution functions at multiple temperatures. A biased potential is quickly generated using this method and is then used in accelerated molecular dynamics simulations.     

A study of microdialysis sampling of metal ions

A study of the extraction fraction (EF) of metal ions Cd, Cr, Cu, Ni and Pb sampled by microdialysis from a quiescent aqueous solution is presented. A concentric type of microdialysis probe equipped with either one of two polysulfone membranes supplied by different manufacturers or a polyether sulfone membrane, all with a 10 mm effective dialysis length was used for these investigations. EF for metal ions achieved after microdialysis sampling were evaluated for membranes exhibiting a cut-off molecular weight of 3, 5, 10 and 30 kDa. The EF for all metal ions showed a dependency on membrane cut-off as well as membrane material. For Cr EFs of 0.70 and 0.80 were achieved at 1 μl/min using a polysulfone and polyether sulfone membrane, respectively, both with a 30 kDa cut-off molecular weight. Using the polysulfone membrane, Cr showed the highest EF and Pb had the lowest at 0.1. The polyether sulfone membrane achieved an EF of 0.95 for Ni and the lowest EF value was for Cu at 0.35. In these studies it is shown that pH as well as the inclusion of an optimal concentration (0.20 M) of 8-hydroxyquinoline (8-HQ) in the perfusion liquid can enhance the EF of metal ions. Microdialysis was also used to sample for metal ions from wastewater and from whole tomatoes grown using sewage sludge manure in order to demonstrate the potential to apply it to these complicated matrices.     

Comparison of extraction methods for sampling of low molecular compounds in polymers degraded during recycling

The demand for mechanical recycling of plastic waste results in an increasing amount of recycled polymeric materials available for development of new products. In order for recycled materials to find their way into the material market, high quality is demanded. Thereby, a complete and closed loop of polymeric materials can be achieved successfully. The concept of high quality for recycled plastics imply that besides a pure fraction of e.g. polyethylene (PE) or polypropylene (PP), containing only minor trace amount of foreign plastics, knowledge is required about the type and amount of low molecular weight (LMW) compounds. During long-term use (service-life), products made of polymeric materials will undergo an often very slow degradation where a series of degradation products are formed, in parallel, additives incorporated in the matrix may also degrade. These compounds migrate at various rates to the surrounding environment. The release rate of LMW products from plastics depends on the initiation time of degradation and the degradation mechanisms. For polymers the formation of degradation products may be initiated already during processing, and subsequent use will add products coming from the surrounding environment, e.g. fragrance and aroma compounds from packaging. During recycling of plastics, emissions which contain a series of different LMW compounds may reach the environment leading to unwanted exposure to additives and their degradation residues as well as degradation products of polymers.Several extraction techniques are available for sampling of LMW compounds in polymers before chromatographic analysis. This paper reviews and compares polymer dissolution, accelerated solvent extraction (ASE), microwave assisted extraction (MAE), ultrasound assisted extraction (UAE), super critical fluid extraction (SFE), soxhlet extraction, head-space extraction (HS), head-space solid phase micro extraction (HS-SPME), and head-space stir bar sorptive extraction (HSSE) as appropriate sampling methods for LMW compounds in recycled polymers. Appropriate internal standards useful for these kinds of matrices were selected, which improved the possibility for later quantification. Based on the review of extraction methods, the most promising techniques were tested with industrially recycled samples of HDPE and PP and virgin HDPE and PP for method comparison.     

Novel method for preparation of cyclodextrin polymers: physico-chemical characterization and cytotoxicity

The objective of this work was to optimize the synthesis procedure of soluble cyclodextrin polymers developed by Weltrowski et al. The use of the parameters indicated by the latter in our laboratory led to a lower result, which did not exceed 15 % (w/w). The new method resulted simultaneously in two fractions, a water soluble one and an insoluble one with a yield of 40 and 85 % (w/w), respectively. Only soluble cyclodextrin polymers were characterized along with the cytotoxicity study. The optimized soluble polymers were characterized by Fourier-Transform Infrared Spectrophotometer, Thermogravimetric Analyzer, Differential Scanning Calorimetry, Powder X-Ray Diffraction Analysis and Size Exclusion Chromatography. In vitro cytotoxicity against peritoneal macrophage cells of female CD1 mice showed that soluble poly-α-CD and poly-γ-CD were less cytotoxic than soluble poly-β-CD at small dose and the opposite was true at higher dose. In conclusion, temperature and time could be used to optimize the yield of polymer cyclodextrins, which will have a broad use in the drug delivery system.     

An in vitro comparison of microdialysis relative recovery of Met- and Leu-enkephalin using cyclodextrins and antibodies as affinity agents

Cyclodextrins and antibodies have been used as affinity agents to improve relative recovery during microdialysis sampling. Two neuropeptides, methionine-enkephalin (ME) and leucine-enkephalin (LE), were chosen to compare the use of cyclodextrins and antibodies as possible affinity agents for improving their relative recovery across polycarbonate and polyethersulfone membranes during in vitro sampling. Cyclodextrins (CD) including β-CD, 2-hydroxypropyl-β-cyclodextrin (2HPβ-CD), and γ-CD gave improvements of relative recovery for both peptides of less than 2-fold as compared to controls. Comparisons of relative recovery between tyrosine–glycine–glycine, tyrosine, and phenylalanine using different cyclodextrins in the perfusion fluid were also obtained. Inclusion of an antibody against met-enkephalin in the microdialysis perfusion fluid resulted in relative recovery increases of up to 2.5-fold. These results show that using antibodies as affinity agents during microdialysis sampling may be more effective agents to improve the relative recovery of these opioid neuropeptides.     

On-line microdialysis for enhanced resolution and sensitivity during electrospray mass spectrometry of non-covalent complexes and competitive binding studies

Many proteins and macromolecules easily form metal adduct ions which impairs their analysis by mass spectrometry. The present study describes how the formation of undesired adducts can be minimized by on-line microdialysis for non-covalent binding studies of macromolecules with low molecular mass ligands with electrospray ionization mass spectrometry (ESI-MS). The technique was indispensable for protein-ligand studies due to reduction of unwanted adduct ions, and thus gave excellent resolution and a sensitivity improvement of at least 5 times. The core of the analytical system was a modified microdialysis device, which was operated in countercurrent mode. A novel technique based on microdialysis for competitive binding studies is also presented. The non-covalent complex between a protein and a ligand was formed in the sample vial prior to analysis. The complex was injected into an on-line microdialysis system where a competitive ligand was administered in the dialysis buffer outside of the fiber. The second ligand competitively displaced the first ligand through transport via the wall of the dialysis fiber, and the intact complexes were detected by ESI-MS.     

Complex formation of unsaturated cyclodextrin solutions with various polymers

By using methyl orange as a competitive complexant, it was shown that solutions of poly(ethylene glycol), poly(propylene glycol) and poly(N-vinylpyrrolidone) equivalent to a concentration of 1.67 mM monomer are able to form soluble inclusion complexes with 0.20 mM solutions of -, - and -cyclodextrins. The complex formation is independent of polymer chain length. Poly(ethylene glycol) solutions complexed, on average with 40%, 45% and 75% of -, -, and -cyclodextrin, respectively. A poly(propylene glycol) solution complexed 55% -cyclodextrin, 80% -cyclodextrin and 90% -cyclodextrin. Poly(N-vinylpyrrolidone) solutions complexed on average with 90% of -, -, and -cyclodextrin.     

Sorption of phenols by single and mixed cyclodextrin polymers

Cyclodextrin (CD) hydrogels were synthesized by a crosslinking reaction with the same cyclodextrin/epichlorohydrin mole ratio (1/11) using αCD, βCD, γCD, and 50:50 mixtures of α/βCD and β/γCD. In order to investigate the sorption capacity of these hydrogels to different solutes, five model molecules have been selected: phenol, 3-nitrophenol, 4-nitrophenol, 1-naphthol, and the antiinflamatory drug diflunisal. The amounts sorbed have been related to the different affinities of the solutes. 1-naphthol shows the highest affinity for these polymers, especially in the case of sorbents containing βCD. The sorption is considerably poorer for phenol than for its nitro derivatives. The two structural isomers 3- and 4-nitrophenol show significant differences in their affinities towards αCD, βCD and α/βCD. Finally, in the case of diflunisal, a bulkier model molecule, remarkable differences were found on the sorption behaviour by polymers whose cyclodextrins have a similar affinity for this solute (βCD, γCD, and β/γCD).     

Complexation behaviour of polymers with pendant cyclodextrin side groups

The influence of the chain conformation on the formation of polymeric supramolecular complexes as well as the influence of the complexation on the conformation of the polymer chain has been studied. The complexation of pyrene into the cavity of β-cyclodextrin (β-CD) was investigated in aqueous solutions of β-CD substituted poly(allylamine) (PAA) under variation of external parameters, i.e. temperature, pH, ionic strength and addition of urea. The observed changes of the complexation constant K for the formation of the 2:1 β-CD/pyrene complex can be explained by a change of the chain flexibility which leads to a variation of the mean distance between neighbouring β-CD-moieties along the polymer chain. The intra-chain association of the decyl group with β-CD in PAA with co-pendant decyl and β-CD is disrupted by the addition of 1-adamantanamine HCl resulting in a more extended structure of the polymer. The β-CD moiety in PAA-CD shows one order of magnitude greater affinity to 2-(p-toluidyl)naphthalene-6-sulfonate than the native β-CD and the affinity increases further by the presence of decyl side groups.