Lipophilic plasticizer

Plasticizer Lipophilicity of plasticizer (log P) Dielectric constant ofplasticizer Water uptake after one week with PVC/plasticizer = 1 2... 

The main classes of plasticizers for polymeric ISEs are defined by now and comprise lipophilic esters and ethers [90], The regular plasticizer content in polymeric membranes is up to 66% and its influence on the membrane properties cannot be neglected. Compatibility with the membrane polymer is an obvious prerequisite, but other plasticizer parameters must be taken into account, with polarity and lipophilicity as the most important ones. The nature of the plasticizer influences sensor selectivity and detection limits, but often the reasons are not straightforward. The specific solvation of ions by the plasticizer may influence the apparent ion-ionophore complex formation constants, as these may vary in different matrices. Ion-pair formation constants also depend on the solvent polarity, but in polymeric membranes such correlations are rather qualitative. Insufficient plasticizer lipophilicity may cause its leaching, which is especially undesired for in-vivo measurements, for microelectrodes and sensors working under flow conditions. Extension of plasticizer alkyl chains in order to enhance lipophilicity is only a partial problem solution, as it may lead to membrane component incompatibility. The concept of plasticizer-free membranes with active compounds, covalently attached to the polymer, has been intensively studied in recent years [91]. 

Recently, Silva et al. have compared several techniques that have been applied to colonial marine invertebrates [13]. Catalan et al. [37] developed a technique in which sponges maintained in aquaria are attached to a plastic plaque. On the plaque, the sponge can be transferred, first to a smaller, aerated, vessel for treatment with an ethanolic or ethereal solution of the desired precursor. Then, after an incorporation period for uptake of the precursor, the sponge is returned to the sea, where metabolism is allowed to proceed in the animal s natural habitat. Silva et al. [13] found that optimal incubation time depended on the sponge, but generally was 20 to 90 days. These authors also reported on the effectiveness of lipophilic compared to hydrophilic precursors the former were taken up and metabolized more efficiently in sponges than hydrophilic ones. 

The optical sensors are composed of ion-selective carriers (ionophores), pH indicator dyes (chromoionophores), and lipophilic ionic additives dissolved in thin layers of plasticized PVC. Ionophores extract the analyte from the sample solution into the polymer membrane. The extraction process is combined with co-extraction or exchange of a proton in order to maintain electroneutrality within the unpolar polymer membrane. This is optically transduced by a pH indicator dye (chromoionophore)10. 

Figure 7. Schematic representation of the microenvironment of the cationic PSD diOC16(3) in a potassium sensor before (A) and after (B) extraction of potassium from the aqueous into the lipophilic membrane phase. The sensor membrane is composed of valinomycin, diOC16(3) and a lipophilic borate salt dissolved in plasticized PVC.

Data are available for plasticizers and ionophores, and indicate the operational stability (the higher the log P value, the higher the lipophilicity). The minimal lipophilicity log P required for membrane components with a lifetime of 30 x 24 h upon exposure to aqueous solution is estimated to be around 10 whereas it has to be as high as 25 for direct measurement in blood, serum and plasma. 

Solvent polymeric membranes, conventionally prepared from a polymer that is highly plasticized with lipophilic organic esters or ethers, are the scope of the present chapter. Such membranes commonly contain various constituents such as an ionophore (or ion carrier), a highly selective complexing agent, and ionic additives (ion exchangers and lipophilic salts). The variety and chemical versatility of the available membrane components allow one to tune the membrane properties, ensuring the desired analytical characteristics. 

Dioctyl sebacate (DOS) with relative permittivity e of 3.9 and 2-nitrophenyl octyl ether (NPOE) with e = 23.9 are the traditionally used sensor membrane plasticizers. The choice of a plasticizer always depends on a sensor application. Thus, NPOE appears to be more beneficial for divalent ions due to its higher polarity, but for some cases its lipophilicity is insufficient. Furthermore, measurements with NPOE-plasticized sensors in undiluted blood are complicated by precipitation of charged species (mainly proteins) on the sensor surface, which leads to significant potential drifts. Although calcium selectivity against sodium and potassium for NPOE-based membranes is better by two orders of magnitude compared to DOS membranes, the latter are recommended for blood measurements as their lower polarity prevents protein deposition [92],... 

Size-related problems may become important for all microsensors. Leakage of sensing materials from a small membrane may lead to rapid deterioration of sensor properties [104], While the lipophilicity of membrane components cannot be increased infinitely, immobilization of ionophore and ion exchanger in the polymer by covalent attachment or molecular imprinting along with utilization of plasticizer-free membranes could help solve the leakage problem. 

Sensors (ion-selective electrodes) incorporating these receptors are typically based on lipophilic membranes made from highly plasticized... 

Bychkova and Shvarev [16] recently prepared nanosensors (0.2-20 pm) for sodium, potassium and calcium using the precipitation method. Similarly to the previous works, the plasticized poly(vinyl chloride) included a phenoxazine chro-moionophore, a lipophilic ion exchanger and a cation-selective ionophore. The dynamic range of the very selective sensors was 5 x 10 4-0.5 M for sodium, 1 x 10 5-0.1 M for potassium and 2 x 10 4 - 0.05 M for calcium. As was demonstrated by Bakker and co-workers [45] a particle caster can be used can be used for preparation of much larger beads (011 pm). 

The polychlorinated biphenyls (PCBs, coplanar biphenyls) have been used in a large variety of applications as dielectric and heat transfer fluids, lubricating oils, plasticizers, wax extenders, and flame retardants. Their industrial use and manufacture in the USA were terminated by 1977. Unfortunately, PCBs persist in the environment. The products used commercially were actually mixtures of PCB isomers and homologs containing 12-68% chlorine. These chemicals are highly stable and highly lipophilic, poorly metabolized, and very resistant to environmental degradation they bioaccumulate in food chains. Food is the major source of PCB residues in humans. 

Studies conducted by different authors on the release of chemical substances from medical devices, mainly those used for infusing solutions, show that these are potential sources of contamination for pharmaceutical formulations. One of the most studied is diethylhexyl phthalate, the same plasticizer found in PVC infusion bags to give flexibility. The same concerns about the use of PVC bags for the storage of lipids or lipophilic formulations are valid for tubing. 

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