text:
|Publication number
|Publication type
|Application number
|Publication date
|Nov 8, 2007
|Filing date
|Nov 10, 2006
|Priority date
|Nov 10, 2005
|Also published as
|Publication number
|Eric Bakker, Yu Qin
|Original Assignee
|Eric Bakker, Yu Qin
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|Referenced by (4), Classifications (5)
|External Links: USPTO, USPTO Assignment, Espacenet
The present application claims priority of U.S. Provisional Patent Application No. 60/735,314, filed on Nov. 10, 2005, the entire contents of which are hereby incorporated herein by reference.
The invention was made in the course of work supported by grant No. BI08-004-00 from the National Science Foundation and by grant Nos. DE14590 and EB002189 from the National Institutes of Health. The United States government has certain rights in this invention.
The present invention is related to systems for detecting target ions in a sample and methods of use thereof in clinical laboratory instrumentation.
Throughout this application, various references are referred to within parentheses. The disclosures of these publications in their entireties are hereby incorporated by reference into this application to more fully describe the state of the art to which this invention pertains. Full bibliographic citation for these references may be found at the end of this application, preceding the claims.
An important sensing platform in ion analyses is the bulk optode, which contains a selective and lipophilic ionophore, a chromoionophore and an ion-exchanger entrapped within a polymeric film coated onto a suitable support. Chromoionophores are normally lipophilic pH indicators used in ion selective optodes. Such dyes usually require sufficient lipophilicity (log PTLC>10.6), a large molar extinction coefficient, a high chemical and photostability and a high selectivity to H+ (1, 2). Chromoionophores may be classified into neutral and charged chromoionophores, depending on the electrical charge of their unprotonated form. In the past two decades, a series of lipophilic H+ selective chromoionophores of different basicities were synthesized (2). The lipophilic H+ selective chromoionophores may be combined with different ionophores to design optodes with different measuring ranges for specific analytical needs (2).
Many of these chromoionophores are highly lipophilic and suitable for general applications. However, optodes based on these chromoionophores exhibit short lifetime in lipophilic samples such as undiluted serum. Further, the leaching of plasticizer and other sensor components is more dramatic when the size of the sensor is reduced to microparticles in the micro-meter range (3) or nanometer range (4, 5). Further, to prevent an inflammable response in in-vivo measurements with such sensors and to avoid cross-contamination between adjacent microspheres, the sensing components including chromoionophores are immobilized onto the polymer matrix.
In earlier work, chromoionophores have been covalently attached onto functionalized poly(vinyl chloride) (6, 7) and onto polyurethane matrices (8), but such polymers could not be used without plasticizer and lead to longer response time. On the other hand, immobilization of non-chromogenic ionophores onto polymers has been more widely studied. Ionophores selective for Na+, K+ and Pb2+ have been covalently grafted to a polysiloxane matrix and applied to the fabrication of CHEMFET sensors (9, 10).
Kimura introduced a sol-gel technique to immobilize ionophores and ion exchangers (11, 12, 13). Another direction in ionophore grafting is to copolymerize the polymerizable ionophores with blank polymers by a one-step solution polymerization method. This type of procedure was utilized for the covalent attachment of two hydrophilic crown ether-type potassium-selective ionophores, 4′-acryloylamidobenzo-15-crown-5 (AAB15C5) and 4′-acryloylamidobenzo-18-crown-6 (AAB18C6) (14, 15, 16), a sodium-selective ionophore, 4-tertbutyl calix[4]arene tetraacetic acid tetraethyl ester (17), a calcium ionophore, N,N-dicyclohexyl-N′-phenyl-N′-3-(2-propenoyl)oxyphenyl-3-oxapentanediamide (AU-1) (16) as well as polymerizable anion ion-exchangers (18) onto an acrylic polymer. The simplicity of this procedure constitutes an important advantage over most other methods described above. These polymers containing grafted ionophores showed comparable selectivity and improved lifetime compared to ISEs based on free, unbound ionophore.
There is a need for improved chromoionophores remedying the defects of the prior art.
The present invention, according to an embodiment, is directed to the synthesis of polymerizable compositions having a pH indicator, a spacer and a polymerizable group. The polymerizable group can be an acrylate or a methacrylate. The spacer can be an oxyalkyl group, an oxypropyl group, or an oxybenzoyl group. The composition can have the structure of NB1 or NB2 shown in
The present invention, according to an embodiment, is also directed to an indicating polymer comprising a copolymer of a composition having a pH indicator, a spacer and a polymerizable group; and a co-monomer. The co-monomer can comprise acrylate or methacrylate. Optionally, the co-monomer comprises methyl methacrylate and decyl methacrylate. Optionally, the co-monomer comprises poly(n-butyl acrylate).
The present invention, according to an embodiment, is also directed to an optode having an indicating polymer, the indicating polymer having: a copolymer of a composition having a pH indicator, a spacer and a polymerizable group; and a co-monomer. The optode can also have a self-plasticizing polymer. The optode can further have a grafted ionophore. Optionally, the optode is a particulate optode.
The present invention, according to an embodiment, is also directed to a method of making a copolymer having selectivity for a target ion. The method includes: providing a monomer having a pH indicator, a spacer, and a polymerizable group; combining the monomer and a co-monomer; and polymerizing the monomer and co-monomer to form a copolymer. The monomer and the co-monomer can be polymerized by thermally initiated free radical solution polymerization.
A better understanding of the present invention will be had with reference to the accompanying drawings in which:
The present invention, according to an embodiment, is directed to synthesis of polymerizable Nile Blue derivatives with acrylic groups and the covalent attachment of the chromoionophores in MMA-DMA or nBA based polymers by simple one step solution polymerization.
Chromoionophores typically have different absorbance and fluorescence spectra when protonated and unprotonated, acting as lipophilic pH indicators. In bulk optodes the change of the protonation and deprotonation of the chromoionophore is related to the change of the activity of the target ions because of a competitive extraction of the two ions into the membrane phase.
Bulk optodes contain long alkyl chains to provide sufficient lipophilicity for regular ion-selective sensors. However, to improve the lifetime of the sensors and eliminate the leaching of the components into lipophilic samples during in-vivo measurements, it is important to covalently graft the chromoionopores. The present invention is directed to polymerizable chromoionophores having pH indicators in combination with spacers and polymerizable acrylic groups for preparing all-polymeric materials and eliminating this leaching problem.
A pH indicator suitable for purposes of this invention is the highly basic oxazine-dye molecule Nile Blue. Nile Blue derivatives such as ETH 5294, ETH 2439, ETH 5350 and ETH 5418, which are shown in
Spacers suitable for purposes this invention include oxyalkyl, oxypropyl and oxybenzoyl groups. Generally, suitable spacers have carbon chains from about 2 to about 18 carbon atoms in length.
The term "polymerizable chromoionophore" refers to a chromoionophore having a polymerizable group, which allows the chromoionophore to become covalently bonded to a copolymer. The polymerizable group is required to allow the chromoionophore to react with a reactive group of the copolymer, such as a carbon-carbon double bond, to form covalent linkages, whereby the chromoionophore becomes covalently grafted onto the copolymer. Examples of such polymerizable groups include, but are not limited to, carbon-carbon double bonds, such as acrylic and methacrlyic groups, carbon-carbon triple bonds and carbonyl groups.
The term "covalently grafted chromoionophore" as used herein refers to a chromoionophore that is attached to a polymer through covalent bonds.
Polymerizable chromoionophores in accordance with the invention can be synthesized, for example, by methods described in the examples below. The method of making the polymerizable chromoionophore will typically include: (1) attaching a spacer to a polymerizable group; and (2) attaching a pH indicating dye, such as a Nile Blue derivative, to the spacer, as described in Example 1.
The terms "polymer" and "copolymer" are used interchangeably and refer to a chemical compound or mixture of compounds formed by polymerization and comprising repeating monomer units, wherein the polymer can comprise one type of monomer unit or can contain two or more different monomer units.
Preferred polymers will have adequate solubility in organic solvents so that they can be mixed with the other components and can be converted into coatings by conventional coating methods. They should furthermore be permeable to ions. The dielectric constant of the polymers is preferably from 2 to 25, particularly preferably from 5 to 15, at 100 Hz and room temperature. The optical transparency is preferably in the range of from about 400 to about 1200 nm, particularly preferably from about 400 to about 900 nm.
Suitable polymers are known to the person skilled in the art. They can be homopolymers, copolymers, block polymers, graft polymers and polymer alloys. The components of a polymer alloy may be a combination of two or more polymer components, said components having high and low glass transition temperatures. The glass transition temperature can be adjusted, for example, by means of the polarity and the chain length and content of structural units. The glass transition temperature is preferably from −130 to 0� C. Polymers with very low Tg values are normally much softer and more difficult to handle mechanically. The Tg is typically determined experimentally with a differential scanning calorimeter, a standard instrument for this purpose.
The polymers can be selected, for example, from the group consisting of polyolefins, polyesters, polyamides, polyethers, polyimides, polyesteramides, polyamideimides, polyurethanes, polyetherurethanes, polyesterurethanes, polyureas, polyurethaneureas and polysiloxanes, it being possible for the polymers to contain ionizable, basic groups (for example amino groups) or ionizable, acidic groups (for example carboxyl or sulfonyl groups), which may be used as replacement for a counterion of lipophilic salts and can provide improved ion transport.
Some examples of monomers for the preparation of polyolefins are C2-C12 olefins, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, C1-C30 esters of acrylic and methacrylic acid, C1-C30 amides of acrylic and methacrylic acid, acrylamide and methacrylamide, vinyl esters of C1-C20 carboxylic acids, acrylonitrile, butadiene, isoprene, chlorobutadiene, styrene, α-ethylstyrene, vinyl chloride, vinyl fluoride, vinylidene chloride and vinyl ethers of C1-C30 alcohols.
Polyesters, polyesteramides and polyamides are preferably synthesized from C2-C12 dicarboxylic acids and C2-C18 diols or -diamines. Polyimides are preferably synthesized from C2-C18 tetracarboxylic acids and C2-C18 diamines. Polyethers are preferably synthesized from aliphatic C2-C12 diols (1,2- or α, ω-lining) or linear adducts of these diols and C8-C30 diglycidyl ethers. Polyurethanes and polyureas are preferably synthesized from C2-C18 diols or -diamines and C2-C20 diisocyanates and/or triisocyanates. Polysiloxanes are preferably synthesized from di(C1-C4)alkylsilyldichlorosilanes
In a preferred embodiment, the polymers comprise a copolymer of methacrylate monomers with different pendant alkyl groups R1 and R2, wherein R1 may be any of C1-3 alkyl group, and R2 may be any of C4-12 alkyl group.
As used herein, the term "alkyl" refers to a saturated linear or branched-chain monovalent hydrocarbon radical of one to twelve carbon atoms, wherein the alkyl radical may be optionally substituted independently with one or more substituents described below. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, isohexyl, and the like
In accordance with embodiments of the present invention, preferably R1 is a C1-2 alkyl group, and R2 is a C8-12 alkyl group. In one embodiment, methyl methacrylate and decyl methacrylate monomers are used for forming a methyl methacrylate-decyl methacrylate (MMA-DMA) copolymer matrix of the present invention.
Methacrylate monomers of the present invention are commercially available from, for example, Polysciences, Inc. (Warrington, Pa.). Alternatively, the methacrylate monomers can be prepared by standard methods known in the art or via thermally initiated free radical solution.
In one embodiment, the chromoionophore monomer comprises a polymerizable group, and the chromoionophore is covalently grafted onto a polymer chain by copolymerizing the chromoionophore monomer with methacrylate co-monomers such as MMA and DMA monomers. In this embodiment, the copolymer may comprise a random distribution of immobilized chromoionophores within the MMA-DMA polymer chain.
Graft copolymers of the present invention comprising a covalently grafted chromoionophore may be made in accordance with methods known in the art or the methods described herein. For example, in one embodiment the graft copolymer is prepared by thermally initiated free radical solution polymerization of a mixture of methacrylate monomers and a polymerizable chromoionophore as described herein in detail in Example 3.
Alternatively, other methods known in the art may be used to covalently graft the chromoionophore. For example, a sol-gel technique may be used to prepare the graft copolymer. Another approach involves directly grafting the chromoionophore onto an existing polymer with active sites. Yet another approach involves blending two different polymers together, with one of them containing the grafted chromoionophore. Alternatively, a solution containing methacrylated monomers and the polymerizable chromoionophore can be irradiated with an electron beam to cause polymerization and covalent attachment of the polymerizable chromoionophore onto the methacrylate copolymer.
A sufficient amount of polymerizable chromoionophore is combined with the copolymer to obtain the desired improvement in desired properties of the copolymer, such as ion selectivity, faster response and recovery times and extended lifetime. Such properties may be quantitatively measured by well-known test methods.
The optimal amount of polymerizable chromoionophore required to produce a significant enhancement of such properties varies depending upon the chemical compositions, structures, and molecular weights of the components employed as well as the extent of grafting achieved. The graft copolymer typically contains the chromoionophore in, for example, an amount from about 0.01% to about 10% by weight, and preferably from about 0.1 to about 5% by weight, based on the amount of polymer. In general, however, it will be advantageous to use at least one part by weight of the polymerizable chromoionophore for every 1000 parts by weight of the copolymer.
The conditions necessary to achieve at least partial grafting of the components of the polymer composition will vary depending upon the reactivities of the individual components. For example, when the chromoionophore comprises polymerizable acrylic groups, the grafting conditions may comprise a thermal or photoinitiated co-polymerization in a solvent such as EtOAc. The graft copolymer will expediently have a mean molecular weight of at least 5,000, preferably at least 10,000 and particularly preferably at least 20,000 daltons, for example from 20,000 to 200,000 daltons, preferably from 50,000 to 200,000 daltons.
In one embodiment, the graft copolymers of this invention may be blended, admixed, or combined with other polymers to obtain blends having improved properties or performance characteristics.
For example, the polymer composition when blended with poly(vinyl chloride) or polyurethane and a plasticizer, such as bis(2-ethylhexyl)sebacate (DOS) or o-nitrophenyloctylether (NPOE), has the beneficial effect of increased mechanical robustness. The relative proportion of PVC polymer:graft polymer composition may be varied as desired, preferably from about 95:5 to about 80:20 on a weight basis.
The graft polymers and blended polymer compositions of the present invention can be adapted for use in a variety of anion-selective sensors capable of detecting the interaction of a target anion with the ionophore. For example, the graft polymers and blended polymer compositions may be used to fabricate ion-selective membranes, films or particles, which include, but are not limited to, carrier-based ion-selective electrodes (ISEs), thin film ion-specific optodes, particle-based optodes, and bulk optodes.
For example, a graft polymer of this invention may be used to fabricate polymer membranes of an ion-selective electrode (ISE) in accordance with methods described in Example 4 of the present invention or any other methods known to one skilled in the art.
Polymers of this invention may also be used to fabricate thin films to be used in a thin film ion-specific optode or to fabricate microsphere particles to be used in particle-based optodes in accordance with methods known in the art. For example, the electrodes and optodes may be prepared by solvent casting and spin coating techniques, as discussed in Examples 5 and 6.
The chromoionophores according to the invention have suitable absorption and emission wavelength ranges that allow the use of known and inexpensive light sources, for example halogen or xenon lamps or light-emitting diodes. Examples of detectors which can be employed are photodiodes. In addition to fluorescence spectroscopy, other optical measurement methods may also be used, for example, absorption spectroscopy.
The ion-detecting sensors of the present invention may be used for detecting ions of all types of body fluid samples. Examples of the samples include, but are not limited to, whole blood, spinal fluid, blood serum, urine, saliva, semen, tears, etc. The fluid sample can be assayed neat or after dilution or treatment with a buffer.
The present invention will be better understood with reference to the following examples and the discussion that follows.
Reagents. 4-hydrobenzonic acid, acryloyl chloride, thionyl chloride, N,N-dimethylformamide, carbon tetrachloride, 2-carboxyethyl acrylate, triethylamine and bis 4 (2-oxo-3-oxazolidinyl)-phosphinic chloride (B0P-C1) were reagent grade from Aldrich (Milwaukee, Wis). Nile Blue chloride salt was obtained from Strem (Newburyport, Mass.). All solvents used for syntheses were obtained from Fisher Scientific (Pittsburgh, Pa.) and dried before using. The monomers methyl methacrylate, 99.5%, n-decyl methacrylate, 99%, n-butyl acrylate, 99%, were obtained from Polysciences, Inc. (Warrington, Pa.). The polymerization initiator 2,2′-azobisisobutyronitrile, 98%, (AIBN) was obtained from Aldrich. Ethyl acetate, dichloromethane and 1,4-dioxane were reagent grade and obtained from Fisher. Inhibitors were removed from the monomers by the reported method (19). AIBN was recrystallized from warm methanol prior to use. 9-(diethylamino)-5-octadecanoylimino-5H-benzo[a]phenoxazine (chromoionophore I, ETH 5294), ter-butylcalix[4]arene-tetrakis(N,N-dimethylthioacetamide) (lead ionophore IV), 4-tert-butylcalix[4]arene-tetraacetic acid tetraethyl ester (sodium ionophore X), sodium tetrakis [3,5-bis(trifluoromethyl) phenyl]borate (NaTFPB), o-nitrophenyloctylether (NPOE), bis(2-ethylhexyl)sebacate (DOS), high molecular weight poly(vinyl chloride), tetrahydrofuran (THF) and all salts were purchased in Selectophore or puriss quality from Fluka (Milwaukee, Wis).
Aqueous solutions were prepared by dissolving the appropriate chloride salts in Nanopure purified water (18 MQ cm).
Synthesis of NB1. Step one: 13.8 g (0.1 mol) of 4-hydrobenzonic acid was dissolved in mixture of a 25 mL carbon tetrachloride and 9.2 g of NaOH in 55 mL water. Subsequently, 0.12 mol of acrylate chloride was added dropwise to the cold mixture. After stirring for 6 h at room temperature, the reaction mixture was neutralized with diluted hydrochloric acid. The resulting precipitate was filtered and washed with warm water, dilute hydrochloric acid, and water. The crude product was recrystallized from ethanol. A white solid powder was obtained (yield 90%).
Step two: 9.6 g (0.05 mol) of 4-acryloyloxybenzoic acid was reacted at 45-50� C. with 30 mL of thionyl chloride containing a few drops of N,N-dimethylfomamide for 10 h, and then the excess thionyl chloride was removed under reduced pressure to give the corresponding acid chloride (yield 85%). Step three: To a solution of 317 mg (1 mmol) of basic Nile Blue in 13 mL of CH2C12, 242 mg (0.8 mmol) of 4-acryloyloxybenzoyl chloride dissolved in 2 mL of CH2Cl2 was added.
After being stirred at room temperature for 15 min, the reaction mixture was diluted with 50 mL of CH2C12 and then washed with 50 mL of 0.1 M NaOH. The organic phase was filtered, the solvent evaporated, and the residue purified by flash chromatography (silica gel, ethyl acetate) and by recrystallization from ethyl acetate to yield 370 mg (0.63 mmol, 40%) of NB1. The structure of NB1 was confirmed by 1HNMR.
Synthesis of NB2. To a solution of 2-carboxyethyl acrylate (0.736 g) and basic Nile Blue (0.529 g) in 30 mL of dry CH2C12 was added Et3N (0.8 g) at room temperature while stirring. Then, 0.612 g of BOP-Cl was added. The mixture was refluxed for 24 h. The reaction mixture was washed with 10 mL of saturated NaHC03 and water. The organic phase was obtained after separation and evaporation of the solvent. The leftover was purified using flash chromatography (1:5 EtOAc:Hexane). A solid was obtained in 31% yield after evaporation of the solvent. The structure of NB2 was confirmed by 1HNMR.
Polymer Synthesis and Characterizations. All polymers were synthesized via thermally initiated free radical solution polymerization. The amount of methyl methacrylate and n-decyl methacrylate used was the same as reported previously (16, 20). For polymers containing grafted ionophores, 1 wt % of Nile Blue derivatives (20 mg), 0.78 g MMA and 0.20 g DMA were dissolved in anhydrous EtOAc. The solution was purged with N2 for 20 minutes before adding 5.1 mg AIBN. The homogeneous solution was continuously stirred and the temperature was ramped to 90� C., which was maintained for 16 h. After the reaction was complete, the solvent was evaporated and the polymer was redissolved in 10 mL of dioxane.
Aliquots of polymer solution (2 mL) were added to 100 mL of distilled water under vigorous stirring. The precipitate was collected and dissolved in 25 mL of dichloromethane, followed by water removal with anhydrous Na2S04 and filtering. The solvent was evaporated and the resultant polymer was washed with methanol to ensure the complete removal of the free ionophores. The polymer was dried under ambient laboratory conditions (yield 80%). The grafted polymers were characterized by H1NMR as reported (21, 22).
The concentrations of grafted dyes were estimated from the H1NMR spectrum to be 40 mmol/kg. For the polymerization with n-butyl acrylate, the EtOAc solution containing 1 g n-BA was heated at 90� C. for 30 min. The reaction temperature was decreased to 60� C. and 25 mg NB2 was added to the solution for another 16 h. This modified procedure was used to prevent the decomposition of the dye. The polymer (yield 60%) was purified and characterized as described above. The concentration of grafted NB2 was estimated from the 1HNMR spectrum to be 40 mmol/kg.
ISE Membrane Preparation and Measurements. ISE membranes were prepared by dissolving chromoionophore (10 mmol/kg), NaTFPB (2 mmol/kg), PVC and plasticizer (DOS or NPOE) to give a total cocktail mass of 140 mg in 1.5 mL of THF. The cocktail of the membrane with grafted chromoionophore contained 2 mmol/kg NaTFPB, 10 wt % MMA-DMA polymer with grafted indicators, PVC and plasticizer (DOS or NPOE). Cocktails were poured into glass rings (2.2 cm i.d.) affixed onto glass microscope slides.
The solvent was evaporated overnight to give a transparent membrane. The parent membranes were then conditioned for at least 12 hours in pH buffered solutions. For pH titrations, buffer solutions are 10 mM citric acid and 10 mM boric acid with the indicated concentrations of NaCl (either 10 mM or 0.1 mM) adjusted to pH 1.5 by 1 M standard HCl, or 10 mM phosphate buffer solution with NaCl as background. The solution was titrated with a 0.1 M standard NaOH solution and a pH electrode was used to monitor the sample pH. All experimental results given are the average of at least three electrodes, with calculated standard deviations.
The sandwich membrane method (23, 24) was used to measure the pKa of the grafted chromoionophores. One single parent membrane contained 10 mmol/kg chromoionophore and 5 mmol/kg NaTFPB in PVC-DOS, PVC-NPOE or MMA-DMA polymer while the other segment contained only NaTFPB in the same matrix. For the grafted ionophore one single membrane contained 1.5 mmol/kg NaTFPB and 10 wt % MMA-DMA-NB polymer in PVC-DOS or blank MMA-DMA while the other one contained the same amount of NaTFPB in PVC-DOS or blank MMA-DMA polymer. The parent membranes were conditioned in citric acid-boric acid buffer solution overnight.
All membrane electrode potential measurements were performed at laboratory ambient temperature in unstirred salt solutions (identical to the conditioning and inner filling solution) versus a Ag/AgCl reference electrode with a 1 M LiOAc bridge electrolyte.
Optode Film Preparation and Measurements. Optode thin films were prepared by spin-coating. The cocktails contained the free or grafted chromoionophores, PVC and plasticizer dissolved in THF. A 200-μL aliquot of the cocktail was transferred with a syringe onto a quartz disk placed in a spin-coating device (1). The resulting 2-3 μm-thick films were equilibrated in different solutions.
The absorbance spectra were recorded with an HP 8452 A diode array spectrophotometer and the fluorescence spectra were recorded by fluorescence microscopy and spectroscopy as previously reported (3, 25). Molar absorption coefficients (e) of NB1 and NB2 were measured in methanol. 2 mL of 2�10 M of NB1 or NB2 in MeOH was placed in a 1-cm quartz cell. The absorption spectrum was recorded after first adding 3 μL of 1 M NaOH and then 10 μL of 1 M HC1 to obtain the unprotonated and protonated form of the chromoionophore, respectively.
For the Pb2+ selective three-component thin-film-based optode, a total of 300 mg of membrane components containing 5 wt % NB1-MMA-DMA, 8.1 mmol/kg NaTFPB, 18.6 mmol/kg Pb (IV) ionophore and PVC/DOS (1:2) were dissolved in 1.75 mL of THF. For the Na+ selective three-component thin-film-based optode, a total of 300 mg of membrane components containing 5 wt % NB2-MMA-DMA, 10 mmol/kg NaTFPB, 20 mmol/kg Na (X) ionophore and PVC/DOS (1:2) were dissolved in 1.75 mL of THF.
The thin films were prepared and characterized by the same spin-coating device and fluorescence microscope described above. All the data points are the average of five measurements, with calculated standard deviations.
Particle preparation and measurement. Plasticizer-free microspheres were prepared with a high-throughput particle casting apparatus previously described (25). The cocktail was prepared by weighing out −2.09 mg (53 mmol/kg) Na ionophore (X), 0.75 mg (21 mmol/kg) NaTFPB, 11 mg grafted NB2 in PnBA (10 mmol/kg) and 25.4 mg blank PnBA dissolved in 1.5 mL cyclohexanone. The mixture was shaken in a vortex mixer for 30 min and than added dropwise to 25 mL dichloromethane under gentle stirring.
After adding 0.5 mL xylenes, the solution was filtered through a 0.45 μm Gelman filter and was transferred to a gastight Hamilton syringe. The syringe containing the polymer core solution was mounted on a syringe pump (Stoelting, Wood Dale, Ill.) and set to flow at a rate of 0.29 mL/min. Deionized water used as the sheath liquid stream flowing at a rate of 43 mL/min was controlled via a pressure regulator. The frequency generator was operated at a setting of 11.9-12.3 kHz.
A borosilicate glass microcapillary of 1.0 mm i.d. and 0.15 mm wall thickness was used for response time measurements. A 50 L aliquot of collected particles was pipetted inside the capillary cell, and the particles were then left to settle for a couple of hours. The capillary was attached at each end with polyethylene tubing, and connected to a peristaltic pump operated at a rate of 0.1 mL/min. Measurements with a fluorescence microscope (3, 26) were taken every 30-60 s or longer thereafter.
The first polymerizable chromoionophore NB1 is a derivative of the highly basic oxazine-dye molecule Nile Blue attached to a acryloyloxybenzoyl group. The pH responses of NB1 based ion selective electrode ("ISE") membranes were investigated first. ISE membranes containing free NB1 were prepared. However, the chromoionophore was found to leach from the membrane during the conditioning step in contact with buffer due to insufficient lipophilicity.
Consequently, an NB1 grafted polymer was prepared by solution polymerization of NB1, MMA and DMA in ethyl acetate and with AIBN as an initiator. The purified polymers were washed, with methanol until the solution remained colorless and indicated the removal of unreacted free NB1 in the polymer. The polymers containing 1 wt % of NB1 were characterized by 1H-NMR. The disappearance of the signals around δ=6.5-7.4 ppm for the double bond of acrylate group confirmed that no free dye was left in the polymer. It was reported earlier that the blending of an ionophore grafted MMA-DMA polymer with other polymers, such as plasticized PVC, exhibits no significant influence on the sensor response but may improve the mechanical stability of the ISE membranes (16). In this work, the same blending method was employed for initial evaluation in ISE membranes. Here, 10 wt % grafted NB1-MMA-DMA was mixed with 90 wt % PVC and DOS (1:2 by mass) to prepare the ISE membranes. No leaching of the dyes was observed during the conditioning and measurements.
The cation selectivity of membranes based on grafted NBl was determined according to the fixed interference method (27) by measuring the pH response curves in a 0.1 M NaCl background. The corresponding logarithmic selectivity coefficient for H+ over Na+ was calculated as log KH,Na pot=−3.1 for PVC-DOS and −5.3 for PVC-NPOE.
The relatively small ion selectivity and narrow pH response range are very different from other reported Nile Blue derivatives. This may be explained by a low pKa value of the chromoionophore or a significant binding affinity to the sodium ion interference. The pKa value of the new dye NBl is expected to be lower than commonly used chromoionophores such as ETH 5294. The carboxyl and benzoyl groups in NBl have a strong electron withdrawing effect and decrease the electron density on the nitrogen of the diethylamino group. The electron on this nitrogen is more delocalized than ETH 5294 and decreases the basicity of the dye.
The apparent pKa values of grafted NBl in the membrane blends were measured by the so-called sandwich membrane method as 4.42�0.05 for PVC-DOS and 7.12�0.02 for PVC-NPOE. These data appear to largely explain the measuring range of membranes containing grafted NBl, but the ester functionality in NBl may also be partly responsible for some alkali metal binding in analogy to earlier work (8, 20).
The low pKa value of NB1 makes it very attractive in optical sensors for measuring transition metal ions at low sample pH. For instance, the fluorescence detection of lead ions at pH 4 aqueous solution had been reported earlier with bulk optodes (26). The optical sensors based on fluorescence measurements have a similar composition as the optodes based on absorbance mode, but require a fluorescence active pH indicator.
The azo dye ETH 5315 exhibits a pKa of 5.5 in optode membranes and would be suitable for heavy metal detection in acidic solution. Unfortunately, it shows very poor fluorescence characteristics. Since Nile Blue derivatives are normally fluorescent, ETH 5418 with a pKa value 8.8 was chosen as an alternative for lead measurement. Unfortunately, the use of ETH 5418 for fluorescence-based measurements requires the development of an inner filter approach since its basic form is not light emitting. Thus, an additional lipophilic reference dye is required.
The fluorescence spectra of grafted NB1 in the polymer matrix is therefore nearly identical to those for the popular dye ETH 5294. These attractive fluorescence characteristics of NB1 and its low pKa make it suitable for measuring lead or other transition metal ions in acidic media. Optical sensors for lead ions were fabricated to evaluate this point. In most cases reported to date, completely plasticizer-free methacrylate copolymer optode films showed slower diffusion behavior and longer response times than plasticized PVC films (28). Acceptably fast response time (<15 min) could be obtained if 10 wt % MMA-DMA polymer with covalently attached ionophore (AU-1) was mixed with DOS-PVC (28). Here, therefore, the Pb+ optode contained Pb-ionophore (IV), ion-exchanger NaTFPB, grafted NB1 in MMA-DMA (5 wt %) and PVC-DOS (1:2 by mass, 90 wt %).
The sensing principle employed to assess optode function is based on an ion-exchange mechanism: (29)
2IndH +(org)+nL(org)+Pb 2+(aq)+2R 31 (org)==2Ind(org)+L n Pb 2+(org)+2H+(aq)+2R −(org) (1)
where Ind is a neutral chromoionophore, L is an ionophore and R− the cation-exchanger, respectively. The organic sensing phase and the aqueous phase are indicated as (org) and (aq). When the optode film comes in contact with lead ions they are extracted into the film and in the process expel hydrogen ions to conserve electroneutrality within the film. The change in the degree of protonation of the fluoroionophore, which is a result of proton release from the film, leads to a measurable change in its fluorescence properties. The response of the films based on an ion-exchange equilibrium, given as a function of the experimentally accessible mole fraction of unprotonated chromoionophore, α, is given as (29):
where LT, CT and RT − are the total concentrations of ionophore, chromoionophore and lipophilic ion-exchanger, respectively, ZI is the charge of the analyte (here ZI=2), n is the complex stoichiometry (here n=1) and kexch is the ion-exchange constant (to describe eq 2).
To realize optical sensors with covalently grafted chromoionophores that may operate at neutral pH, the second polymerizable chromoionophore, NB2, was synthesized. The free NB2 was found to be more lipophilic than NBl since no obvious leaching was observed for an ISE membrane containing freely dissolved NB2. The pH responses of free NB2 in PVC-DOS and PVC-NPOE membranes were measured, as shown in
NB2 based membranes gave Nernstian response ranges from pH 6 to 10 for DOS membranes and from pH 5 to 11 for NPOE membrane. The logarithmic selectivity coefficients for H+ over Na+ were found as −10.3 for DOS membranes and <−11 for NPOE membranes containing free NB2. The pKa values of free NB2 in DOS and NPOE membranes determined by the sandwich method were determined as 10.10�0.02 (DOS) and 12.49�0.02 (NPOE), which are just somewhat smaller than those of ETH 5294 (11.4 and 14.8, respectively, with the same method. The difference may be caused by the inductive effect of the ester in NB2 which is not present in ETH 5294.
NB2 was covalently grafted into a MMA-DMA polymer matrix by the same solution polymerization method used above.
For grafted NB2-MMA-DMA membrane the logarithmic selectivity coefficient for H+ over Na+ were found as −8.8 for DOS membrane and −9.3 for NPOE membrane. The somewhat diminished selectivity compared to membranes containing free NB2 may be partly explained by the influence of the methacrylate type copolymer, which possesses some ion binding properties originating from its ester functionalities. The absorbance properties of NB2 were characterized in THF solutions as shown in
The results indicate that the covalent attachment does not change the fluorescence properties of the chromoionophore and that grafted NB2 may be used as a H+-fluoroionophore for the detection of fluorescence ratios with optodes measured at neutral pH. In example 5, Na-selective optode thin films were prepared. The films contained NB2-MMA-DMA, sodium ionophore Na—X and NaTFPB. The sensing principle employed to assess optode function is based on the same basic ion-exchange mechanism described above (with zI=1 and n=1 in eq 2).
The response curve of an optode film towards Na+ and the corresponding selectivity behavior are presented in
In past studies, completely plasticizer-free methacrylate copolymer optode films often showed slower diffusion behavior and much longer response time than plasticized PVC films. The response time of microspheres composed of MMA-DMA was found to be as long as 12 h (28). To shorten the response time Poly n-butyl acrylate (PnBA) may be used as "internal plasticizer" for preparing plasticizer-free sensors. Due to its low Tg and high fluidity, PnBA alone is not suitable for making ISE membranes but has to be used together with other, higher Tg polymers. However, poly(n-butyl acrylate) was found to be suitable for the preparation of plasticizer-free microspheres and the diffusion is rapid in this matrix.
In example 6, poly(n-butyl acrylate) with grafted NB2 was prepared by copolymerization of NB2 and n-butyl acrylate, in EtOAc. The resulting PnBA particles were mass fabricated using a high-throughput particle casting apparatus previously described (25).
The particles have the same selectivity sequence as the thin film-based optodes. The exchange constants and selectivities are also very similar to thin film optodes, suggesting that the particles function in complete analogy to the thin films.
Two polymerizable Nile Blue derivatives (NB1 and NB2) were synthesized. They exhibit similar absorbance and fluorescence spectra as the established Nile Blue derivative ETH 5294. The structural variations between the two dyes results in widely different pKa values and a large shift in the measuring range of the resulting sensing films. Upon covalent attachment of the dyes in the polymer matrix, the new materials may be successfully used as pH indicators and fluoroionophores in ion-selective optodes.
NB1-MMA-DMA exhibits a low pKa value and two fluorescence emission peaks, and appears to be a better suited chromoionophore than ETH 5418 for the fabrication of transition metal selective optodes operating at low pH values and/or low analyte concentrations. NB2-MMA-DMA blended with PVC-DOS or NPOE is suitable for preparing ion-optodes used at near-neutral pH for the measurement of more abundant ions (especially alkali and alkaline earth metal ions).
NB2 can also be copolymerized with PnBA to prepare polymers with faster response times. The first reported hydrophobic bulk optodes containing a grafted NB2 and no plasticizer were prepared using NB2-MMA-DMA and exhibited a functional Na+ response according to classical optode theory, with fast response times. The selectivity observed over common interferences such as Ca, K+, and Mg+ was found to be high.
Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions described herein.
All features disclosed in the specification, including the claims, abstracts and drawings, and all the steps in any method or process disclosed, may be combined in any combination except combination where at least some of such features and/or steps are mutually exclusive. Each feature disclosed in the specification, including the claims, abstract, and drawings, can be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
Any element in a claim that does not explicitly state "means" for performing a specified function or "step" for performing a specified function, should not be interpreted as a "means" or "step" clause as specified in 35 U.S.C. �112.
1. Seiler, K.; Simon, W., Sens. Actuators B 1992, 6, 295-298.
2. Bakker, E.; Lerchi, M.; Rosatzin, T.; Rusterholz, B.; Simon, W., Anal. Chim. Acta 1993,278,211-225.
3. Tsagkatakis, I.; Peper, S.; Retter, R.; Bell, M.; Bakker, E., Anal. Chem. 2001, 73, 6083-6087.
4. Brasuel, M.; Kopelman, R.; Miller, T. J.; Tjalkens, R.; Philbert, M. A., Anal. Chem. 2001, 73,2221-2228.
5. Brasuel, M.; Kopelman, R.; Philbert, M. A.; Aylott, J. W.; Clark, H.; Kasman, I.; King, M.; Monson, E.; Sumner, J.; Hoyer, M.; Miller, T. J.; Tjalkens, R., Optical Biosensors 2002, 497-536.
6. Lindner, E.; Rosatzin, T.; Jeney, J.; Cosofret, V. V.; Simon, W.; Buck, R., /. Electroanal. Chem. 1993, 352, 309-312.
7. Lindner, E.; Cosofret, V. V.; Kusy, R. P.; Buck, R. P.; Rosatzin, T.; Schaller, U.; Simon, W.; Jeney, J.; Toth, K.; Pungor, E., Talanta 1993,40, 957-967.
8. Puntener, M.; Fibbioli, M.; Bakker, E.; Pretsch, E., Electroanalysis 2002, 14, 1329-1338.
9. Reinhoudt, D. N.; Engbersen, J. F. J.; Brzozka, Z., Anal. Chem. 1994, 66, 3618-3623.
10. Hogg, G.; Lutze, O.; Cammann, K., Anal. Chim. Acta 1996, 335, 103-109.
11. Kimura, K.; Sunagawa, T.; Yokoyama, M., Anal. Chem. 1997, 69, 2379-2383.
12. Kimura, K.; Sunagawa, T.; Yajima, S.; Miyake, S.; Yokoyama, M., Anal. Chem. 1998,70,4309-4313.
13. Kimura, K.; Yajima, S.; Takase, H.; Yokoyama, M.; Sakurai, Y., Anal. Chem. 2001,73, 1605-1609.
14. Heng, L. Y.; Hall, E. A. H., Electroanalysis 2000, 12, 178-186.
15. Heng, L. Y.; Hall, E. A. H., Electroanalysis 2000, 12, 187-193.
16. Qin, Y.; Peper, S.; Radu, A.; Bakker, E., Anal. Chem. 2003, 75, 3038-3045.
17. Malinowska, E.; Gawart, L.; Parzuchowski, P.; Rokicki, G.; Brzozka, Z., Anal. Chirn. Acta 2000,421, 93-101.
18. Qin, Y.; Bakker, E., Anal. Chem. 2003, 75, 6002-6010.
19. Horn, M. B., Acrylic Resins, Reinhold Publishing Corp.: New York, 1960.
20. Qin, Y.; Peper, S.; Bakker, E., Electroanalysis 2002, 13, 1375-1382.
21. Heng, L. Y.; Hall, E. A. H., Anal. Chim. Acta 2001, 443, 25-40.
22. Qin, Y.; Bakker, E., Anal. Chem. 2004, 76, 4379-4386.
23. Mi, Y.; Bakker, E., Anal. Chem. 1999, 71, 5279-5287.
24. Qin, Y.; Bakker, E., Talanta 2002, 58, 909-918.
25. Tsagkatakis, I.; Peper, S.; Bakker, E., Anal. Chem. 2001, 73, 315-320.
26. Telting-Diaz, M.; Bakker, E., Anal. Chem. 2002,74, 5251-5256.
27. Bakker, E.; Biihlmann, P.; Pretsch, E., Chem. Rev. 1997, 97, 3083-3132.
28. Peper, S.; Ceresa, A.; Qin, Y.; Bakker, E., Anal. Chim. Acta 2003, 500, 127-136.
29. Lerchi, M.; Bakker, E.; Rusterholz, B.; Simon, W., Anal. Chem. 1992, 64, 1534-1540.
30. Shortreed, M.; Bakker, E.; Kopelman, R., Anal. Chem. 1996, 68, 2656-2662.
31. Seiler, K.; Simon, W., Anal. Chim. Acta 1992, 266, 73-87.
32. Chan, W. H.; Lee, A. W. M.; Lee, C. M.; Yau, K. W.; Wang, K., Analyst 1995, 120, 1963-1967.
|Citing Patent
|Filing date
|Publication date
|Oct 30, 2008
|Jan 24, 2012
|Kimberly-Clark Worldwide, Inc.
|Training progress indicator
|Aug 6, 2010
|Apr 28, 2015
|Kimberly-Clark Worldwide, Inc.
|Absorbent articles with intricate graphics
|Dec 18, 2008
|Jul 2, 2009
|Nellcor Puritan Bennett Llc
|Carbon dioxide detector having an acrylic based substrate
|Aug 6, 2010
|Apr 3, 2012
|Kimberly-Clark Worldwide, Inc.
|Wetness indicator
|U.S. Classification
|524/90, 524/556
|International Classification
|Cooperative Classification
|European Classification


text:
Munsterman has also confirmed that the club is prepared to sell the 24-year-old defender before the transfer window closes.
Douglas' current contract with Twente is set to expire next summer.
"Both clubs (Fulham & Newcastle) told us they want to do business with us," Munsterman told Voetbal International.
"We didn't received any offers yet, but when they want to pay a fair price, Douglas may leave the club. Because otherwise he will leave Twente for free next year."
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Who of Europe's top strikers will move to England this summer?
After a dreadful start to their Bundesliga campaign, Borussia Dortmund appear to have weathered the storm after going five matches without defeat.

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FIA launches crackdown on human traffickers, 24 held- Gujrat/Gujranwala—Federal Investigation Agency (FIA) arrested four outlaws involved in human trafficking and recovered fake passports and others documents during separate actions here on Tuesday. According to details, the FIA teams in its ... Pakistan Observer, 1 week ago
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Federal agency plans briefing on deadly Seattle bus crash; 15 people remain hospitalized
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All was excellent. The location, the accommodations, gourmet food and the employees. Just sitting on the porch viewing the outstanding scenery was super. We hiked to several scenic lakes & other sites. Lots of hiking.
I've never before had to park 12 miles from my lodging, but this sure was worth the trip! The view from the front porch? One of the best I've ever seen. And staying at the lodge gives you a great launch point for day hikes into the high Sierras.
Lodging: Two of us shared 1 of 6 canvas tents at...
An incredible experience from the time you start your hike in. Food is amazing and staff really cares. The best place ever to get an emotional reset. Best to stay for a couple of days so you can take advantage of the great day hikes to Tamarack or Hamilton Lake.
cant wait to head back. amazing staff and beautiful setting. we hiked during the day and watched the stars at night. the food was also delicious which is surprising when in the back country. you will not go wrong spending a few nights here.
A great place to experience the Sierras in comfort, warm bed and hot showers. A charming six tent camp with great views and a friendly staff. Don't miss the hike to Hamilton Lakes, one of the best hikes and views in California on the High Sierra Trail.
Chad and his crew are receptive and provide delicious meals to Vegans and vegetarians!! The shower really does have hot water and the toilet shed is kept quite clean. Watching the moon rise over the ridge is an event that will stay with you forever...
A shout out to the best most accommodating creative and friendly staff ever; Michelle, Vince and Chad. You made our stay even as special and unique as the view. We have specific dietary restrictions and they have limited resources (all supplies are brought in by mule). When we made the reservations we weren't sure if they could accommodate our diet....
My business partner and I started up a company and we named it Sequoia Commercial Lending. We just celebrated our first year in business, so we thought it would be fitting to head up to the Sequoias to celebrate. We did a little research and found out about the High Sierra Camp. We were lucky to find a reservation mid...
Bearpaw is always a great treat! Beautiful place with gracious hosts, a nice group of other guests, and comfortable accommodations. I recommend to stay at Bearpaw after having backpacked for several days. Very nice experience! For people who'd like to do a few day hikes at Sequoia, Bearpaw is also a great starting place.
So welcoming and always a incredible stay. Chad (Manager) , Brian, Michelle, and the wonderful chef make it a such an memorable stay. Thank you! Plan on starting the hike at Crescent Meadow early so you can arrive by late afternoon for the shower.


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Stephen Curry could become the first player in NBA history to defeat all four of his fellow All-NBA First Team members in the playoffs.
Curry and the Golden State Warriors swept Anthony Davis and the New Orleans Pelicans, followed by a six-game series win over Marc Gasol and the Memphis Grizzlies.
The Warriors are now one win away from defeating James Harden and the Houston Rockets.
The Cleveland Cavaliers and LeBron James are one win away from The Finals as well. This would also be first time in 30 years that the NBA's MVP faces the second- and third-place finishers. In 1985, Larry Bird faced second-placed Magic Johnson in The Finals after earlier meeting third-placed Moses Malone.


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It's been a couple years since the divorce. It was a nice break to get myself sorted out and really focus on being a dad. Now I'd like to share some of my time with someone special. While I'm not sure how I feel about jumping right back into a serious relationship, I'd like to start by meeting someone, making connections and seeing where things go from there. And don't worry - The last thing I'm looking for is a rebound relationship. :)
I think it's safe to describe me as stable, secure, level headed and kind. Does this make me too much of a square, lol? I am literally an Eagle Scout after all. Funny, when I was growing up I always wanted to be the Han Solo type but knew I was much more Luke Skywalker. (Square and a nerd I guess).
I don't like games or drama - but then again who admits that they do? I also don't consider myself the "extreme" type. It seems like there are a lot of those profiles on this site. I love to hike, bike and swim but I don't have a lot of pictures as proof. I laughed when I saw so many pics of "dudes" showing their abs when I went looking at my competition. Isn't it more fun to find out what's under someone's shirt in person? Besides pics can lie :). Oh, and yes I do look good with my shirt off, lol ;).
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Python Developer
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I'm experience Python specialist, I have experience of analysing, designing, developing and implementing ERP system project since 2011, especialy OpenERP project. I have strong background knowleage of sale, hr and CRM modules. I also wrote many Independent addon modules on OpenERP, I can make a project come true from out of nothing. I can work independently with high pressure under limited working time. I think I'm hard-working developer and never-miss-deadline spirit is my another strength. Thank you for paying some time dropping by!


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Join us on Saturday, October 10th for Pet Friends Wine Tasting. Live entertainment, appetizers, music, and wine at our Main Winery location in Irwin, PA.
Swing by the Main Winery in Irwin and treat yourself! Local salons and boutiques will be showing off their products while we serve wine and other appetizers.
Come Wine Down at our Main Winery. Enjoy pizza, wine, and the fall weather after work this September
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Bruce Maiorana
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Hey there, I'm Bruce, thank you for visiting my CS profile.
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It's a good project
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I discovered hitchhiking was possible
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knocking on the door was possible and there are nice people everywhere
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I could teach a few asian and european languages and always carry some dices with me d10, d20, d4, d6 so can teach you to play rpgs if you are interested.I'm trying to write a diary, so I could share that with you.And we could share some beers at the park?
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Fantasy Football Fantasy - …
JOHNSTOWN — The winners never even took the ice Tuesday night.
Walt Rucosky spends part of his day with mushrooms.
"Turn Back the Hands of Time," a concert presented by Michael Facciani, will be performed at the Pasquerilla Performing Arts Center on the University of Pittsburgh at Johnstown campus Sept. 30 beginning at 7:30 p.m.
Hannah Cotchen played her first volleyball match in the seventh grade, and has committed herself to the sport ever since. The 17-year-old senior at Bishop Carroll Catholic High School plays the outside hitter position for the lady Huskies.
Johnstown native Kevin Gleason used a quick-thinking maneuver late in the race to earn his second victory this season Sept. 19 in the TCR Inte…
Similar to the field corn and soybeans grown at Weakland Farms, autumn activities held there started small, but continue to grow and expand.
A local pageant contestant is taking her platform of healthy living and sharing it with the local teens that she works with.
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Please weigh in on this debate regarding the U.S. currency.
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1833 Horseshoe Pike In Honey Brook. Rt 322. App...
- 88.00 Acres
Honey Brook, PA
1833 Horseshoe Pike In Honey Brook. Rt 322. Approximate 54.4 Acres For Sale In West Brandywine To...
Exton is located in West Whiteland Township, Chester County, Pennsylvania. Its population was 4,842 at the 2010 census. The Exton Square Mall and Main Street at Exton are both located within Exton along with several other shopping centers, making Exton... Read More
West Chester is a borough and the county seat of Chester County, Pennsylvania in the U.S. state of Pennsylvania. The population was 18,461 at the 2010 census. West Chester University of Pennsylvania is located in the borough. Valley Forge, the Bran... Read More
Chadds Ford Township is a township in Delaware County, Pennsylvania, United States, about 30 miles southwest of Philadelphia. Prior to 1996, Chadds Ford Township was known as Birmingham Township, and the name was changed to allow the township to corres... Read More
Limerick Township is a township in Montgomery County, Pennsylvania. It was named for the hometown of early settler William Evans, whose family arrived in the area from Limerick, Ireland in 1698. The township is mentioned in Philadelphia court records ... Read More
Wyomissing is a borough in Berks County, Pennsylvania, United States, established on July 2, 1906. As of the 2010 census the population was 10,461, compared to 8,587 at the 2000 census. The population growth of the borough was largely due to its merger... Read More
Whether you're taking that first step into real estate or an experienced investor, we can help! Springer Realty Group has been growing nicely since 2009, opening offices in Exton, Limerick and Wyomissing. SRG takes great pride in being a reliable, locally owned, non-franchise business serving all of Pennsylvania's home and property needs.
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© 2015 TREND, All Rights Reserved. Information Deemed Reliable But Not Guaranteed.
The data relating to real estate for sale on this website appears in part through the TREND Internet Data Exchange program, a voluntary cooperative exchange of property listing data between licensed real estate brokerage firms in which Springer Realty Group participates, and is provided by TREND through a licensing agreement.
The information provided by this website is for the personal, non-commercial use of consumers and may not be used for any purpose other than to identify prospective properties consumers may be interested in purchasing.
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Listing information last updated on October 9th, 2015 at 3:47pm UTC.


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We fell in love with this darling duo a couple of weeks ago when we featured their amazing wedding film by FortyOneTwenty. So in love, in fact, that sharing even more of their dream day seemed like a total no-brainer. Especially sinceRead More On SMP
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By Catholic Online (NEWS CONSORTIUM)
7/10/2013 (2 years ago)
Catholic Online (www.catholic.org)
Archbishop Jose Gomez, is asking Catholics to oppose an insidious new law that purports to protect children, but actually does little to help them. Instead, the law is a cleverly-disguised attack on the Church and has little to do with children and everything to do with church property and finances.
By Catholic Online (NEWS CONSORTIUM)
Catholic Online (www.catholic.org)
7/10/2013 (2 years ago)
Published in Living Faith
Keywords: Church, lawsuits, statute of limitations, SB 131, Archbishop Gomez
LOS ANGELES, CA (Catholic Online) - California Senate Bill 131 would eliminate for one year, the statute of limitations on civil suits against the Catholic Church brought by alleged victims of childhood abuse. This would allow child victims to sue their perpetrator's employers for damages.
Statutes of limitations exist for a reason. They encourage the presentation of legal claims within a reasonable amount of time. They generally ensure that the parties involved are living and have recent, important memory of events that are alleged to have transpired. They also prevent endless harassment of a party.
However, the law as currently proposed exclusively targets privately run institutions. In other words, it does not target public institutions where children became victims of abuse - only private ones, which happen to be, in large proportion, Catholic or religious institutions.
Ultimately, the bill is designed to give the outward appearance of being "for the children" in order to build support. However, it may not even be used by any children or their families. Instead, adults will have an open season where they may freely accuse the church of being a party to abuses that may or may not have actually happened decades ago. Such an open door leaves the church with no choice but to fight or settle, which will add a massive financial burden to an already financially strained church.
A growing number of the opponents of the Catholic Church believe that Churches and religious institutions should be taxed on their income and contributions. The current bill seems to be another indication of a growing hostility to the Catholic Church and religious institutions.
The Church needs to minister effectively to the poor, the disenfranchised, as well as children and adults, including those who are being well-educated at Catholic institutions. The Church does not possess endless reserves of cash to pay clever lawyers representing clients who may or may not have actually faced abuse with no protection such as a statute of limitations.
The Church has made it clear, over the past several years, that the abuse of children, or of adults,by members of the Clergy is reprehensible, evil, and will not be tolerated. Under Archbishop Gomez and Pope Francis, any vestiges of protection for would-be abusers has been stripped away and such individuals have no place to hide. Any accusations will be reported to police and perpetrators will face prompt arrest.
In cases where the Church followed outdated policies which did in fact cause harm to children, the Church has paid, and will continue to satisfy legal claims.
However, an open season on the Church is a bad idea. The law does not require the proof of a prior criminal case to permit a claim, so anyone who wished to do so could make such an accusation.
The policy is also discriminatory as it does not entitle anyone else to bring such claims, which renders its motives suspect.
The Catholic Church, in standing against anti-life proponents and the Obama regime, continues to draw the ire of powerful elites who want to undermine its ability to stand as a major force for morality and good. However, these attacks are not unexpected, for the enemies of the Church have always been present and have always schemed against Her.
Despite this, the Church remains protected by the promises of Christ. SB 131 is just the latest manifestation of a greater evil, dressed in such a way as to make it appealing for all.
Will you defend your church?
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By Hannah Marfil (CALIFORNIA NETWORK)
Life struggles are inevitable but to look at them more than just a bump in the road is like putting rocks in your backpack before a hike. God doesn't want that - our journey to Him is meant to shape us in a way He planned for us. Little by little, we achieve victories ... continue reading
By Elise Harris, CNA/EWTN News
Family rescues us from indifference and loneliness and teaches us the essentials of life, Pope Francis said - adding that as the family of God, the Church has the same role and must evaluate how to live this out. Vatican City (CNA/EWTN News) - "Like Saint ... continue reading
By Tony Magliano
For the sake of our salvation, we need to pay serious attention, and act with purpose, to what Jesus teaches here in Matthew's Gospel: "When the Son of Man comes in his glory, and all the angels with him, he will sit upon his glorious throne, and all the nations will ... continue reading
By Linky C. (NEWS CONSORTIUM)
12-year-old Julia Bruzzese, who has been experiencing symptoms of Lyme disease, suffered from sudden paralysis that doctors are still unable to explain. However, following a blessing from Pope Francis, the young girl seems to be healing. NEW YORK, NY (Catholic Online) ... continue reading
By Elise Harris, CNA/EWTN News
Pope Francis formally opened the synod of bishops Sunday, telling participants that the union between a man and woman is the foundation of God's plan for the family, and a solution to the many forms of loneliness in today's world. Vatican City (CNA/EWTN News) - ... continue reading
By Catholic Online (NEWS CONSORTIUM)
Presiding over a prayer vigil in St. Peter's Square, Pope Francis led the beginning of the Extraordinary Synod of Bishops on the Family, at the Vatican. Drawing tens of thousands of the faithful, many were present in the Square since the afternoon for a ... continue reading
By CNA/EWTN News
The director of the Holy See press office has issued a statement in response to Vatican official Msgr. Krzysztof Charamsa's declaration in a recent interview that he is homosexual and has a boyfriend. Vatican City (CNA/EWTN News) - Msgr. Charamsa, 43, granted a ... continue reading
By CNA/EWTN News
Each of us has a Guardian Angel who, acting on behalf of God, advises us and protects us from evil, if we only listen to him, Pope Francis said during his homily at Mass on Friday. Vatican City (CNA/EWTN News) - "May we ask the Lord for the grace of this ... continue reading
By Kenya Sinclair (NEWS CONSORTIUM)
What makes you angry? Maybe you don't like the way your boss talks to you at work or your spouse spends too much money. What do you do when you feel anger coming on? Who do you turn to? LOS ANGELES, CA (Catholic Online) - When we get angry we can say or do things we ... continue reading
By Linky C. (NEWS CONSORTIUM)
Megachurch Pastor Kyle Idleman claims that to live life, "everyone simply needs to get over themselves" to truly "experience abundant life with Jesus," a theory he promotes in his new book The End of Me: Where Real Life in the Upside-Down Ways of Jesus Begins. LOS ... continue reading


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Six Feet Under
American Death Metal legends SIX FEET UNDER return to mainland Europe early December for the 'X-Mas in Hell Tour 2015'!Read More
Twitching Tongues
Southern California's rising underground metal/hardcore band Twitching Tongues has unveiled a new song called 'Sacrifice Me' today at NPR.org.Read More
Mother Feather
Mother Feather has released the title track from their full length debut, 'Mother Feather'! The song is available now on iTunes, and the video is streaming at metalblade.com/motherfeather.Read More
The Black Dahlia Murder
The Black Dahlia Murder debut at #45 on the Billboard Top 200 Chart and at #66 on the official German album charts! See below for all first week charting specifics.Read More
Denner / Shermann
Denner / Shermann EP 'Satan's Tomb' will be released on October 2nd via Metal Blade Records. The title track has been finally released and is streaming online now at metalblade.com/dennershermannRead More
Culture Killer
Florida's Culture Killer announced their signing with Metal Blade Records in May of this year. Now, they are finally poised to launch their campaign for their debut full length, 'Throes of Mankind.'Read More
New Releases
Upcoming Releases
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THEORIES Stream New Album in Full at Invisible Oranges
- 19/03/15 – "Regression" To See European Release This...Read More
Between the Buried and Me announce "Coma Ecliptic" album and tour
- 19/03/15 – The first single from and pre-orders for "Coma...Read More
Metal Blade to re-issue classic HEXX albums 'No Escape' and 'Under The Spell' on vinyl!
- 18/03/15 – To commemorate the return of the great HEXX, Metal Blade...Read More
APOPHYS: Dutch Death Metal Legion Unleashes New Single From Debut Full-Length Via No Clean Singing
- 16/03/15 – A word derived from Apophis, an asteroid that, upon...Read More
Sweden's SORCERER Premiere New Song On The Obelisk
- 12/03/15 – New Album In The Shadow Of The Inverted Cross Out March...Read More
MOTOR SISTER premiere video for 'A Hole' on Billboard.com!
- 12/03/15 – "All you really need to know about Ride is that it...Read More
FALCONER announces re-issue of debut album!
- 11/03/15 – "Ultimate Edition" of "Falconer"...Read More
SIX FEET UNDER announces Victor Brandt on bass to step in for HATEFEST tour 2015 featuring Marduk and Vader among others!
- 10/03/15 – April 2015 will see the return of the HATEFEST Tour. The...Read More


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SPE NL Presents:
Monthly meeting Monday, 12th of October 2015
"Improving Capital Expenditure Efficiency"
By Ruud Schulte (EBN)
Read more & Register here
Upcoming Event
SPE-NL Presents:
Dutch Hydrocarbons Symposium
Tuesday 13 October, 13:00 – 18:00hrs | Amsterdam RAI
Co-located with Offshore Energy Exhibition & Conference
Register now for the Dutch hydrocarbons symposium organized by the Society of Petroleum Engineers – Netherlands Section. The symposium will discuss the state of play in Dutch hydrocarbons and also commemorates the 55th anniversary of SPE-NL. Against the backdrop of declining oil and gas prices and declining production, the program focuses on what is needed – ranging from innovations in technology to changes in work processes and regulations – to make better use of the gas reserves of the North Sea. The symposium will also address what the industry has learned from previous downturns and how uneconomic opportunities can be turned into economic ones.
Symposium program
13.00 – 13.00 Welcoming coffee
13.30 – 13.40 Welcome by the symposium chair
Lex de Groot, Head of Exploration and Asset Management, ENGIE E&P Nederland
13.40 – 14.00 Setting the scene: A history of oil and gas price developments
Jan-Hein Jesse, Jesco
14.00 - 14.20 Setting the scene: State of play and challenges in Dutch hydrocarbons
Lucia van Geuns, Sr Consultant Petroleum Geosciences, TNO/Chair, KNGMG
14.20 – 14.40 Innovations in production engineering
Speaker TBD
14.40 – 15.00 Innovations in offshore engineering: Rig free well intervention
Speaker TBD, Weatherford
15.00 – 15.20 Innovations and cost savings in work processes
15.20 – 15.50 Refreshment break
15.50 – 16.10 Innovations in UK regulations
Carlo Prochettini, Oil & Gas Authority UK (invited)
16.10 – 16.30 Non-operated venture management
Eric van Ewijk, Asset Manager, EBN
16.30 – 16.50 Intergenerational Panel
Panel discussion with speakers, a student and a YP
16.50 – 17.00 Closing remarks
17.00 – 18.00 Networking drinks
The fee for attending is EUR 30 ex VAT for SPE members and non-members. The student fee is EUR 10 ex VAT.
The SPE-NL symposium is co-located with Offshore Energy Exhibition & Conference. To register:
Discount on technical sessions
* SPE members receive a 50% discount on the Offshore Energy technical sessions (regular fee €75 ex VAT per session) for example on HPHT developments or Subsea Processing. SPE student members receive a 75% discount. You can book your technical sessions at step 3 in the registration. To claim your 50% discount enter SPE50 at Step 5 Payment. To claim your 75% discount enter SPE75 at Step 5 Payment. SPE membership will be verified. More information on the technical sessions: http://offshore-energy.biz/conference/conference-program-1/
Check out all planned activities in the SPE NL AGENDA
SPE Peer-Review Papers
SPE's peer review process provides invaluable constructive feedback from experts in your field, allowing you to make a good paper even better.
Learn more.
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ContentNews Features Press Releases Solicitations Events
#Newcomicsday is 10/7
Welcome to The i Word, the official podcast of Image Comics, hosted by David Brothers. In creator-owned comics, the creator is the real star, and the goal of the podcast is to not just talk comics with one creator at a time, but to give you a chance to see what influences them, too. For the first half of the show, we'll talk about their comics work. We'll discuss their process, collaborators, upcoming work, and other things related to their books. After that's done, we'll switch gears and talk about something they're passionate about, be it sports, video games, movies, or obscure b-sides from an ultra-specific microgenre of music. My guest this week is Sloane Leong, co-creator of FROM UNDER MOUNTAINS with Marian Churchland and Claire Gibson.
This episode is focused on Leong's work with Churchland and Gibson on FROM UNDER MOUNTAINS. In this all-new fantasy series, old feuds and new monsters rise up to haunt the isolated northern fortress of Karsgate. At the center of the series are three people—a knight, a thief, and royalty—who will be forced to confront this conflict in a variety of ways. Leong took her inspiration for the look of the series from a variety of cultures, and works closely with the co-writing team of Churchland and Gibson to create a fantasy story that is a breath of fresh air. We close the show with a discussion of Sloane's interest in exploring the movies, books, and music created specifically by people of color, particularly those of Polynesian descent or focus.
FROM UNDER MOUNTAINS #1 is on-sale now. FROM UNDER MOUNTAINS #2 releases 10/28.
Permalink: https://imagecomics.com/features/the-i-word-sloane-leong-on-from-under-mountains-people-of-color-in-fiction
Latest News
BIRTHRIGHT gets oversized issue to kick off new story arc
Each issue of this new arc will feature "Hero's Journey" variants, iconic moments in Mikey's life depicted by Image's finest artists
October 6, 2015
WAYWARD takes off in a new story arc
Collect all five issues in this story arc to fit them into a massive WAYWARD illustration
October 5, 2015


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Samsung Galaxy Tab 10.1 Reviews
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Latest News for the Samsung Galaxy Tab 10.1
Korean government disappointed Obama did not veto Samsung sales ban
The Korean Herald reports that the Korean government is disappointed the Obama government did not veto the ITC?s (US International Trade Commission) decision to enforce a sales ban on Samsung products such as the Samsung Galaxy S, the Samsung Galaxy S2, the Samsung Galaxy Nexus, and the Samsung Galaxy Tab 10.1.
US Trade Representative Michael ... Read moreSales ban on Samsung Galaxy Tab 10.1 in US to be lifted
An injunction banning the sale of the Samsung Galaxy Tab 10.1 in the US could be lifted. According to Reuters, Judge Lucy Koh has now been given the green light to rule on the issue.
A US court of appeal ruled that the ban on the 10-inch tablet should be reconsidered by the lower court. ... Read moreIce Cream Sandwich finally rolls out to Samsung Galaxy Tab range
Samsung has finally started rolling out the Android 4.0 (Ice Cream Sandwich) update to its Galaxy Tab range. According to Pocket-lint, these include the Galaxy Tab 7.7, Galaxy Tab 8.9, and Galaxy Tab 10.1. The ICS update for the Tab 10.1 is now available.
If you own a Galaxy Tab 10.1, the update is available ... Read moreUK judge orders Apple to publicly apologise to Samsung
UK Judge Colin Birss has ordered Apple to publicly apologise to Samsung, admitting that the Korean tech giant?s Galaxy Tab did not copy the design of the iPad. The apology will be in the form of newspaper ads. Furthermore, Apple must keep the apology on their website for six months.
In the US, a judge ... Read moreApple gets Samsung Galaxy Nexus banned in the US ? joins Galaxy Tab 10.1
Another one bites the dust. Apple previously had the Samsung Galaxy Tab 10.1 banned in the US. Now, it has done the same to the Galaxy Nexus. Not only does this look bad for Samsung, it also looks bad for Android.
In patent-related courtroom battles, pre-trial injunctions are rare. Apple, however, managed two pre-trial injunctions ... Read moreApple gets Samsung Galaxy Tab 10.1 banned in the US
Apple (makers of the iPhone) has managed to temporarily ban the sale of the Samsung Galaxy Tab 10.1 in the US. A US judge ruled that the Korean tech giant?s tablet may infringe on iPad patents. While a decision is being made, the judge has ordered the sales ban of Samsung?s 10-inch Android tablet.
The ... Read moreUS court denies Apple?s request to ban the sale of the Samsung Galaxy Tab 10.1
Apple?s request to have the Samsung Galaxy Tab 10.1 banned for being sold in US shops has been denied by a California district court. This is the second time the Cupertino firm tried to ban the iPad 2?s rival. The first attempt was made in December, which was denied by Judge Lucy Koh.
Judge Koh?s ... Read moreApple attempts to ban the Galaxy Tab 10.1 in the US right before its scheduled peace talks with Samsung
According to Foss patents, Apple has filed for a sales ban of the Galaxy Tab 10.1 in the US just days before its scheduled peace talks with Samsung.
This is not the first time Apple tried to ban the Korean tech giant?s tablet. It successfully enforced an injunction against the device in Germany. Samsung then ... Read more


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My review
Original recipe yields 4 servings
Based on a 2,000 calorie dietSee full nutrition
Ready In
This is great if you add 3 chopped chicken breast to sauce
My favorite is the Best Marinara Yet on this site. This one is good too, just a little plain and my fiance said too tangy.
My favorite is the Best Marinara Yet on this site. This one is good too, just a little plain and my fiance said too tangy.
I was very disappointed in this sauce. A few more herbs would make the difference I think. I probably won't make it again.
This is a great sauce particularly becacuse it's not runny. I used mine for meatloaf sandwiches so I was looking for somehting thick. The extra freezes well and complements bread sticks or che...
This is a great base recipe to bend and make more personal. I sauteed fresh minced onion in with the garlic and I added a good amount of basil and oregano as well as red pepper flake and a pinch...
I used concentrated crushed tomatoes for a smoother sauce in this recipe. I added a small amount of sauteed garlic and italian seasonings. It still was a little bland to me. I will continue t...
a really great sauce! i like lots of spices so to this recipe by the letter, i added fresh basil, oregano and marjoram from my herb garden. I also grow parsley, so that was fresh as well. My ...
Quartering the tomatoes so that they melt into the sauce is an improvement, but this is an excellent sauce.
Mamma mia! This is-a mighty pizza sauce! It was like making sweet love to a tomato all over again. So tasty, it brought me way back to the good olden days, a week ago (sigh). It was a very d...


text:
She did a great job on my face, she came to my place and was knowledgable in what he does! I will use her again!Like this review?Yes|Flag Abuse
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Select your all-time Springbok dream team and stand a chance to win R3 000 in cash!
Get Sport24 on your mobile
Sharks CEO John Smit has a message for disappointed Sharks fans after the team's failure to reach the Currie Cup semi-finals.
Sharks captain Marco Wentzel and Director of Rugby Gary Gold have apologised to fans after they failed to reach the Currie Cup semis.
The Free State Cheetahs booked their spot in the semi-finals of this year's Currie Cup after their final group stage match against the Sharks ended...
Leopards coach Robert du Preez has been linked with a coaching role at the Sharks.
Sharks Director of Rugby Gary Gold has named his team for their clash against the Free State Cheetahs in Bloemfontein.
The Sharks and the Cheetahs meet in what is effectively a Currie Cup quarter-final in Bloemfontein on Saturday night.
Free State Cheetahs coach Franco Smith has named his team for their crucial Currie Cup clash against the Sharks in Bloemfontein.
Griquas were no match for a rampant Sharks side during their Absa Currie Cup match at Griqua Park in Kimberley on Saturday.
Sharks Director of Rugby Gary Gold has named his team to tackle Griquas in a Currie Cup clash in Kimberley.
The Lions will make history by becoming the first team to play a Super Rugby match in Japan when the 18-team competition kicks off.
The Blue Bulls have beaten the Sharks in their Currie Cup clash at Kings Park in Durban.
As they prepare to face the Sharks in Durban, the Blue Bulls are eager to return to the form they displayed earlier in the Currie Cup.
The Blue Bulls will be eager to get back to winning ways when they tackle the Sharks in a Currie Cup clash in Durban.
Blue Bulls coach Nollis Marais has named his team to tackle the Sharks in a Currie Cup clash in Durban.
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The Single Worst Line of Dialogue in the entire Star Trek Franchise
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August 24 2013, 09:08 PM
Fleet Captain
Location: At star's end.
Re: The Single Worst Line of Dialogue in the entire Star Trek Franchis
Anwar wrote:
They already knew the Feds weren't under Borg control, and there were plenty of non-Borg species in our Universe when they said that "The Weak Shall Perish" thing. They KNEW and still said that. So they were okay killing us all even though we had nothing to do with the Borg.
Sure, they never said it in "In the Flesh" but they did already know when they said it in "Scorpion".
Their behaviour in 'In the flesh' makes 8472 a far more reasonable species than the borg could ever hope to be.
In 'Scorpion', 8472 was pissed off - with good reason.
Let truth and falsehood grapple ... Truth is strong" - John Milton
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