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MAA
Selected AbstractsA Biomimetic Potentiometric Sensor Using Molecularly Imprinted Polymer for the Cetirizine Assay in Tablets and Biological FluidsELECTROANALYSIS, Issue 18 2008Mehran Javanbakht Abstract Despite the increasing number of applications of molecularly imprinted polymers (MIPs) in analytical chemistry, the construction of a biomimetic potentiometric sensor remains still challenging. In this work, a biomimetic potentiometric sensor, based on a non-covalent imprinted polymer was fabricated for the recognition and determination of cetirizine. The MIP was synthesized by precipitation polymerization, using cetirizine dihydrochloride as a template molecule, methacrylic acid (MAA) as a functional monomer and ethylene glycol dimethacrylate (EGDMA) as a cross linking agent. The sensor showed high selectivity and a sensitive response to the template in aqueous system. The MIP-modified electrode exhibited Nernstian response (28.0±0.9 mV/decade) in a wide concentration range of 1.0×10,6 to 1.0×10,2 M with a lower detection limit of 7.0×10,7 M. The electrode has response time of ca. 20,s, high performance, high sensitivity, and good long term stability (more than 5,months). The method was satisfactory and used to the cetirizine assay in tablets and biological fluids. [source] Novel Potentiometric Sensors of Molecular Imprinted Polymers for Specific Binding of ChlormequatELECTROANALYSIS, Issue 2 2008Ayman Abstract Molecularly imprinted polymers (MIP) were used as potentiometric sensors for the selective recognition and determination of chlormequat (CMQ). They were produced after radical polymerization of 4-vinyl pyridine (4-VP) or methacrylic acid (MAA) monomers in the presence of a cross-linker. CMQ was used as template. Similar non-imprinted (NI) polymers (NIP) were produced by removing the template from reaction media. The effect of kind and amount of MIP or NIP sensors on the potentiometric behavior was investigated. Main analytical features were evaluated in steady and flow modes of operation. The sensor MIP/4-VP exhibited the best performance, presenting fast near-Nernstian response for CMQ over the concentration range 6.2×10,6,1.0×10,2,mol L,1 with detection limits of 4.1×10,6,mol L,1. The sensor was independent from the pH of test solutions in the range 5,10. Potentiometric selectivity coefficients of the proposed sensors were evaluated over several inorganic and organic cations. Results pointed out a good selectivity to CMQ. The sensor was applied to the potentiometric determination of CMQ in commercial phytopharmaceuticals and spiked water samples. Recoveries ranged 96 to 108.5%. [source] Mercury Detection in Seawater Using a Mercaptoacetic Acid Modified Gold Microwire ElectrodeELECTROANALYSIS, Issue 10 2005Antje Widmann Abstract It is demonstrated here that it is possible to determine mercury in chloride containing media like seawater by anodic stripping voltammetry using a modified electrode. A gold microwire electrode is modified using mercaptoacetic acid (MAA) to eliminate the problem of calomel formation, allowing the mercury to become fully removed from the electrode surface after each scan. In a synthetic salt solution of KNO3 the sensitivity for mercury was found to be improved by the surface modification. In seawater the sensitivity was not significantly improved possibly because of complexation of the mercury by the abundant chloride; however, the MAA coating prevented the formation of calomel causing the background scan to be free of mercury. Measurements in seawater at various pH values demonstrated that mercury detection is possible at natural pH (around 8); however, best sensitivity was attained at pH,4.8 with a deposition time of 3,min. A peak for copper occurred at more negative potential but did not interfere at this pH. The calibration was linear between 0 and 37,nM mercury with a limit of detection of 1,nM mercury. [source] (S)-Ibuprofen-imprinted polymers incorporating ,-methacryloxypropyl-trimethoxysilane for CEC separation of ibuprofen enantiomersELECTROPHORESIS, Issue 21 2006Qi-Liang Deng Abstract In this report, a novel preparation method of molecularly imprinted polymers (MIPs) for CEC was developed. Molecularly imprinted monolithic columns for (S)-ibuprofen were prepared and evaluated, in which charged entities responsible for establishing EOF have been derived from ,-methacryloxypropyltrimethoxysilane (,-MAPS), which was hydrolyzed following copolymerization with 4-vinylpyridine (4-VPY) and ethylene glycol dimethacrylate,(EDMA). The EOF and molecular recognition of the stationary phase were investigated in aqueous and nonaqueous media, respectively. The experimental results indicated that the material showed a reasonably stable EOF and the prepared separation materials were capable of separating racemic ibuprofen, a task that could not be accomplished by MIPs prepared in parallel, using methacrylic acid (MAA) as a functional monomer. The efficiency at pH,3.2 for the first-eluted enantiomer and the last-eluted enantiomer (the imprinted analyte) were 128,700 and 2100,plates/m, respectively. [source] Enhancement of the NAD(P)(H) Pool in Escherichia coli for BiotransformationENGINEERING IN LIFE SCIENCES (ELECTRONIC), Issue 4 2007F. Heuser Abstract In pyridine nucleotide-dependent, reductive whole cell biotransformation with resting cells of Escherichia coli, the availability of intracellular NAD(P)(H) is a pivotal point for an efficient and highly productive substrate conversion. The question whether an increase of the intracellular NAD(P)(H) concentration could increase the productivity was discussed controversially in the past. This is the first report on an E. coli strain with an increased NAD(P)(H) pool which was tested in a reductive biotransformation system for an increased productivity. Biotransformation was performed with a strain overexpressing a gene encoding an (R)-specific alcohol dehydrogenase for the stereospecific, NADPH-dependent reduction of methyl acetoacetate (MAA) to (R)-methyl-3-hydroxybutanoate (MHB). Cofactor regeneration was implemented via glucose oxidation by coexpression of a gene encoding glucose dehydrogenase. The specific MHB productivity (mmol mg,1 cell dry weight,1h,1) enabled a comparison between the E. coli,BL21(DE3) wild-type and a genetically modified strain. The enhancement of the NAD(P)(H) pool was achieved by genetic manipulation of the NAD(H) biosynthetic pathways. After simultaneous overexpression of the pncB and nadE genes, encoding nicotinic acid phosphoribosyltransferase and NAD synthetase, measurements of the total NAD(P)(H) pool, sizes showed a 7-fold and 2-fold increased intracellular concentration of NAD(H) and NADP(H), respectively. However, the implementation of an E.,coli strain carrying a genomically integrated pncB gene with an upstream T7,promoter for biotransformation did not result in reproducible increased specific cell productivity. [source] Expression of melanoma-associated antigens in melanoma cell culturesEXPERIMENTAL DERMATOLOGY, Issue 7 2005Mirjana Urosevic Abstract:, The efficiency of melanoma immunotherapy appears to depend on both melanoma- and immune system-specific factors. Melanoma-specific factors include melanoma-associated antigen (MAA) expression as well as HLA class I molecule expression. We investigated the expression of five MAA , Melan-A/MART-1, tyrosinase, gp100, MAGE-1 and MAGE-3 , by means of FACS analysis in 50 melanoma cell cultures and compared them to the cultures of human foreskin-derived melanocytes and melanoma cell line UKRV-Mel2. Melan-A, tyrosinase and gp100 expression was frequently reduced in melanoma cell cultures, compared to that in foreskin melanocytes, whereas MAGE-1 and MAGE-3 expression showed variable degree of upregulation, compared to that in foreskin melanocytes. The expression of all tested MAA demonstrated high interindividual variability. We further show that cell cultures derived from the same tissue sample are oligoclonal in nature, by demonstrating the presence of up to three cell populations bearing distinct MAA profile. Analysing samples derived from the same patient but each at a different time point, we show that MAA expression profile changes over time either in positive (increase) or in negative (decrease) direction. Finally, we demonstrate that brain metastasis-derived cell cultures significantly overexpress Melan-A and MAGE-3, compared to primary tumours and other metastatic sites (P -value range: 0.05,0.001). Elucidation of the MAA expression patterns and the kinetics within the same patient as well as during the course of the disease may help improve current and develop new immunotherapeutic strategies. [source] Tolerance of Antarctic cyanobacterial mats to enhanced UV radiationFEMS MICROBIOLOGY ECOLOGY, Issue 1 2001Alison L. George Abstract To assess the biological implications of ozone depletion over the Antarctic Peninsula, the ultraviolet (UV) regime of two Antarctic cyanobacterial communities (composed of Leptolyngbya sp. and Phormidium sp.) was manipulated using screens that cut out UV radiation and a lamp which enhanced the dose of UV-B radiation (280,315 nm). The biological response of the cyanobacterial mats was monitored by measurement of chlorophyll fluorescence and pigment concentrations. The Leptolyngbya mat showed significant photochemical inhibition due to increased UV-B relative to photosynthetically active radiation (400,700 nm). The effect of UV on the Phormidium mat was less pronounced and dependent on the method of analysis: significantly lower photochemical yields were observed in UV-enhanced Phormidium mats compared to UV-excluded treatment, but if the yield data relative to the time zero control were considered then no effect of UV enhancement was observed. The Phormidium mat contained over 25 times the absolute concentration of UV-protecting mycosporine-like amino acid (MAA) and double the concentration of carotenoids compared to the Leptolyngbya mat, but the latter contained a higher ratio of carotenoids+MAAs to chlorophyll. There were no significant treatment-related changes in the concentrations of MAA, carotenoids and chlorophyll a in the Phormidium mat. The Leptolyngbya mat showed significantly lower chlorophyll a concentrations under UV enhancement, which could account for the lower photochemical yield in this sample. Our results show that different cyanobacterial species have differing photochemical sensitivity to UV-B radiation, which may confer a subtle advantage to the UV-B tolerant species over the less tolerant type during a period of high UV-B irradiance. [source] Delivery of Nucleic Acids through the Controlled Disassembly of Multifunctional NanocomplexesADVANCED FUNCTIONAL MATERIALS, Issue 24 2009Mahmoud Elsabahy Abstract In this study, novel pH-responsive polyion complex micelles (PICMs) were developed for the efficient delivery of nucleic acid drugs, such as antisense oligonucleotide (AON) and short interfering RNA (siRNA). The PICMs consisted of a poly(amidoamine) (PAMAM) dendrimer,nucleic acid core and a detachable poly(ethylene glycol)- block -poly(propyl methacrylate- co -methacrylic acid) (PEG- b -P(PrMA- co -MAA)) shell. The micelles displayed a mean hydrodynamic diameter ranging from 50 to 70,nm, a narrow size distribution, and a nearly neutral surface charge. They could be lyophilized without any additives and stored in dried form. Upon redispersion in water, no change in complexation efficiency or colloidal properties was observed. Entry of the micelles into cancers cells was mediated by a monoclonal antibody fragment positioned at the extremity of the PEG segment via a disulfide linkage. Upon cellular uptake and protonation of the MAA units in the acidic endosomal environment, the micelles lost their corona, thereby exposing their positively charged endosomolytic PAMAM/nucleic acid core. When these pH-responsive targeted PICMs were loaded with AON or siRNAs that targeted the oncoprotein Bcl-2, they exhibited a greater transfection activity than nontargeted PICMs or commercial PAMAM dendrimers. Moreover, their nonspecific cytotoxicity was lower than that of PAMAM. The pH-responsive PICMs reported here appear as promising carriers for the delivery of nucleic acids. [source] Preparation and Characteristics of Esculin-Imprinted PolymersHELVETICA CHIMICA ACTA, Issue 6 2007Guo-Song Wang Abstract Four molecularly imprinted polymers (MIPs) were prepared in MeOH with esculin (=6,7-dihydroxycoumarin 6-(, - D -glucopyranoside)=6-(, - D -glucopyranosyloxy)-7-hydroxy-2H -1-benzopyran-2-one) as the imprinted molecule, methacrylic acid (=2-methylprop-2-enoic acid; MAA), acrylamide (=prop-2-enamide; AM), 4-vinylpyridine (=4-ethenylpyridine; 4-VP), or 2-vinylpyridine (=2-ethenylpyridine; 2-VP) as the functional monomer, respectively, as well as ethylene glycol dimethacrylate (=2-methylprop-2-enoic acid ethane-1,2-diyl ester; EGDMA) as the cross-linking agent. The interaction between the template and the functional monomers was investigated by fluorescence and UV spectrophotometry, respectively, which revealed the presence of esculin/monomer complexes in the stoichiometric ratio 1,:,2 in the pre-polymerization mixture. The resultant polymers were studied in equilibrium binding experiments to evaluate the recognition ability and the binding capacity towards esculin. The results showed that MIP1, prepared with MAA as the functional monomer, exhibited advantageous characteristics of high binding capacity, optimal imprinting effect, and good selectivity towards esculin. The Scatchard analysis indicated that there are two types of binding sites in MIP1, and its binding parameters including the apparent maximum numbers of binding sites and the dissociation constants were calculated. Finally, by packing an SPE column (SPE=solid-phase extraction) with MIP1, the esculin was separated and enriched successfully by this sorbent from samples of Cortex fraxini, and the average recovery was up to 74.7%. [source] The Stereostructure of Porphyra-334: An Experimental and Calculational NMR Investigation.HELVETICA CHIMICA ACTA, Issue 3 2007Evidence for an Efficient, Proton Sponge' Abstract The mycosporine-like amino acid (MAA) porphyra-334 (1) is subjected to extensive 1H- and 13C-NMR analysis as well as to density-functional-theory (DFT) calculations. All 1H- and 13C-NMR signals of 1 are assigned, as well as the resonances of prochiral proton pairs. This is achieved by 500-MHz standard COSY, HMQC, and HMBC experiments, as well as by one-dimensional (DPFGSE-NOE) and two-dimensional (NOESY) NOE experiments. Diffusion measurements (DOSY) confirm that 1 is monomeric in D2O solution. DFT Calculations yield 13C-NMR chemical shifts which are in good agreement for species 6 which is the imino N-protonated form of 1. An exceptionally high proton affinity of 265.7,kcal/mol is calculated for 1, indicating that 1 may behave as a very powerful ,proton sponge' of comparable strength as synthetic systems studied so far. Predictions of 13C-NMR chemical shifts by the ,NMRPredict' software are in agreement with the DFT data. The absolute configuration at the ring stereogenic center of 1 is concluded to be (S) from NOE data as well as from similarities with the absolute configuration (S) found in mycosporine-glycine 16. This supports the assumption that 1 is biochemically derived from 3,3- O -didehydroquinic acid (17). The data obtained question the results recently published by a different research group claiming that the configuration at the imino moiety of 1 is (Z), rather than (E) as established by the here presented study. [source] Kinetic Study of the Asymmetric Hydrogenation of Methyl Acetoacetate in the Presence of a Ruthenium Binaphthophosphepine ComplexADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009Eva Öchsner Abstract The asymmetric hydrogenation of methyl acetoacetate (MAA) in methanol using dibromobis{(S)-4-phenyl-4,5-dihydro-3H -dinaphtho[2,1- c: 1,,2,- e]phosphepine}-ruthenium was studied in detail. For the determination of the reaction network, data from kinetic experiments were compared to different possible reaction networks using the kinetic software Presto Kinetics. The simulation was optimised to describe the reaction accurately with a minimal set of process parameters and reaction equations. For the best model the reaction orders, collision factors and activation energy of all reaction steps were determined. Additionally, the influence of reaction temperature and hydrogen pressure on the enantiomeric excess (ee) of the reaction was studied. It was found that high reaction temperatures and high hydrogen pressures result in increasing enantioselectivities. [source] The role of auxiliary monomers and emulsifiers on wet scrub resistance of various latex paints at different pigment volume concentrationsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2009M. Khorassani Abstract This work is an attempt to study the effect of different latex types containing various auxiliary monomers and emulsifiers on their pigmentation and their corresponding behavior on scrub resistance. The auxiliary monomers investigated were acrylic acid (AA), methacrylic acid (MAA), and itaconic acid and the emulsifiers contained sodium lauryl sulfate (SLS) and sodium dodecylbenzene sulfonate (SDBS). It was shown that a semibatch polymerization technique which led to smaller particles and sharper size distributions is preferable. The best wet scrub results were obtained by using MAA and SLS. It was also shown that the proper selection of an auxiliary monomer generally depended on the range of incorporated pigment volume concentration (PVC). At high PVCs, AA gave better performances compared with MMA. The reverse effect was shown to occur at low PVCs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Photografting of acrylic acid and methacrylic acid onto polyolefines initiated by formaldehyde in aqueous solutionsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2009Jianmei Han Abstract Formaldehyde aqueous solution can act as an effective photoinitiating system for water-borne photografting. The photografting of acrylic acid (AA) and methacrylic acid (MAA) onto high-density polyethylene (HDPE), low-density polyethylene (LDPE) and polypropylene (PP) initiated by formaldehyde aqueous solutions has been reported. The effects of formaldehyde content and monomer concentration on grafting varied with the polymeric substrates and monomers used. For the grafting of AA onto HDPE, the extent of grafting increased with increasing formaldehyde content in the solution, monomer concentration had a little effect on grafting. Whereas for the grafting of MAA onto HDPE, the grafting performed in 8% formaldehyde aqueous solution lead to the highest extent of grafting, the extent of grafting increased with monomer concentration till 2.5 mol/L. MAA was easier to be grafted onto the polyolefins than AA. The easiness of grafting occurring on the polyolefins was in a decreasing order of LDPE > HDPE > PP. Qualitative and semi-quantitative Fourier transform infrared (FTIR) characterizations of the grafted samples were performed. For both grafted LDPE and PP samples, at the same irradiation time, the carbonyl index of the samples grafted with MAA was higher than that grafted with AA. The FTIR results are in accord with the results obtained by gravimetric method. The water absorbency of the grafted samples increased almost linearly with the extent of grafting. The PE films grafted with AA adsorbed more water than those grafted with MAA. This study had broadened the water-borne initiating system for photografting. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Antimicrobial finishing of regular and modified nylon-6 fabricsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 2 2008S. E. Shalaby Abstract A simple, efficient, and practically applicable functional approach for improvement antimicrobial properties of nylon-6 fabrics and increase the washing durability of biofunctions was developed. This finishing approach is based on grafting of the fabrics with methacrylic acid (MAA) to create additional carboxylic groups in nylon-6 macromolecules, followed by subsequent reaction with dimethylalklbenzyl ammonium chloride (DMABAC) solution under alkaline conditions. The carboxylic groups react with cationic agent through ionic interaction, which led to the immobilization of QAS on nylon-6 fabrics. This immobilization was proofed through determination of nitrogen content, applying scanning electron microscopy (SEM), and FTIR microscopy. The effect of treatment conditions on salt uptake (SUT) on nylon-6 fabrics and reaction efficiency (RE) was investigated. The antimicrobial assessment of regular and grafted with PMAA nylon-6 fabrics treated with DMABAC revealed that both types of fabrics are characterized before washing, by quite strong biocide effect on Bacillus mycoides, Escherichia coli and Candida albicans. The role of grafting nylon-6 fabrics before treatment with salt on durability of antimicrobial functions seems to be more significant as the samples were repeatedly washed. Even after Laundring 10 times the grafted samples could still provide 80%, 100%, and 87.5% microbial reduction against B. mycoides, E. coli and C. albicans, respectively, in contrast with 42.6%, 65.6%, and 42.5% in case of regular nylon-6 fabrics. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008. [source] Release behavior of freeze-dried alginate beads containing poly(N -isopropylacrylamide) copolymersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2008Jae-Hyung Choi Abstract Beads composed of alginate, poly(N -isopropylacrylamide) (PNIPAM), the copolymers of N -isopropylacrylamide and methacrylic acid (P(NIPAM- co -MAA)), and the copolymers of N -isopropylacrylamide, methacrylic acid, and octadecyl acrylate (P(NIPAM- co -MAA- co -ODA)), were prepared by dropping the polymer solutions into CaCl2 solution. The beads were freeze-dried and the release of blue dextran entrapped in the beads was observed in distilled water with time and pH. The degree of release was in the order of alginate bead < alginate/PNIPAM bead , alginate/P(NIPAM- co -MAA) bead < alginate/P(NIPAM- co -MAA- co -ODA) bead. On the other hand, swelling ratios reached steady state within 20 min, and the values were 200,800 depending on the bead composition. The degree of swelling showed the same order as that of release. Among the beads, only alginate/P(NIPAM- co -MAA- co -ODA) bead exhibited pH-dependent release. At acidic condition, inter- and intraelectrostatic repulsion is weak and P(NIPAM- co -MAA- co -ODA) could readily be assembled into an aggregate due to the prevailing hydrophobic interaction of ODA. Thus, it could block the pore of bead matrix, leading to a suppressed release. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Preparation and cytocompatibility of chitosan-modified polylactideJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2008Yumei Xiao Abstract Chitosan-modified PLA (CMPLA) was fabricated to improve cytocompatibility of polylactide (PLA). PMAA-grafted PLA (PMAA-PLA) was obtained through ,-methacrylic acid (MAA) grafted polymerization on PLA surface with photooxidization and UV irradiation. Steady PMAA-PLA microparticle suspension with an average size as 172.8 ± 3.6 nm and zeta potential as ,95.0 ± 0.6 mV was prepared through solvent volatilization. By static electricity interaction and other interactions between PMAA-PLA microsparticles and chitosan molecules, CMPLA was obtained. FTIR, XPS, SEM, and zeta potential analyses indicated that CMPLA was modified with chitosan molecules uniformly. Compared with the PLA control, CMPLA adapted to supporting the attachment and proliferation of L929 cells better. The obtained CMPLA was expected to be used as perfect biomaterial for tissue regeneration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Increased sialylation of polymeric ,-IgA1 in patients with IgA nephropathyJOURNAL OF CLINICAL LABORATORY ANALYSIS, Issue 1 2002Joseph C.K. Leung Abstract The mechanism of mesangial IgA deposition is poorly understood in IgA nephropathy (IgAN). Abnormal glycosylation of carbohydrate moieties in the hinge region of the IgA molecule has recently attracted much attention. In this report, we studied galactosylation and sialylation profiles in ,- and ,-IgA1 from patients with IgAN. Total serum IgA1 was isolated from patients with IgAN or healthy controls by jacalin-affinity chromatography. Six fractions of molecular weight (MW) 50,1,000 kDa were separated by fast protein liquid chromatography (FPLC). Four lectin-binding assays were used to study the sialylation and the presence of terminal galactose or N-acetylgalactosamine (GalNAc) in the O-linked carbohydrate moieties of ,- or ,-IgA1. Maackia amurensis agglutinin (MAA) and Sambucus nigra agglutinin (SNA) lectin recognize ,(2,3)- and ,(2,6)-linked sialic acid, respectively. Peanut agglutinin (PNA) and Helix aspersa (HA) lectin recognize terminal galactose and GalNAc, respectively. Reduced HA was demonstrated in macromolecular , or ,-IgA1 (300,825 kDa) isolated from patients with IgAN (P < 0.05 compared with healthy controls). Lambda- but not ,-IgA1 from patients with IgAN bound less to PNA (P < 0.05). The ,(2,3)-linked sialic acid content in ,- but not ,-IgA1 of MW 150,610 kDa from patients was higher than that of controls (P < 0.005). The ,(2,6)-linked sialic acid content in ,-IgA1 (300,825 kDa) and ,-IgA1 (150,610 kDa) from patients was also higher than that of controls. This unusual glycosylation and sialylation pattern of the ,-IgA1 may have important implications for the pathogenesis of IgAN, as both the masking effect of sialic acid on galactose and the reduced galactosylation will hinder the clearance of macromolecular ,-IgA1 by asialoglycoprotein receptor of hepatocytes. The negative charge from sialic acid may also favor mesangial deposition of macromolecular ,-IgA1 in IgAN. J. Clin. Lab. Anal. 16:11,19, 2002. © 2002 Wiley-Liss, Inc. [source] Enhancing therapeutic loading and delaying transport via molecular imprinting and living/controlled polymerizationAICHE JOURNAL, Issue 1 2010Asa D. Vaughan Abstract This work demonstrates for the first time molecular imprinting using a "living/controlled" polymerization (LCP) strategy to enhance template loading/affinity and delay release in weakly crosslinked gels. Two gel systems were studied: poly(DEAEM- co -HEMA- co -PEG200DMA) gels imprinted for diclofenac sodium and poly(MAA- co -EGDMA) gels imprinted for ethyl adenine-9-acetate. Experimental evidence confirms that template diffusion coefficients within imprinted gels can be heavily influenced by template binding affinity. Recognition studies revealed significant increases in template loading/affinity with large increases in loading for LCP, and dynamic template release studies showed that imprinting via LCP extends the template release profile by twofold over that of imprinting via conventional free-radical polymerization techniques and fourfold over the control network (less Fickian and toward zero-order release with a profile coefficient of 0.70). Analysis of reaction kinetics indicated that LCP with reversible termination events increases the chemically controlled chain propagation mechanism, and that binding sites are formed during this phase of the polymerization. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] Introduction of pH-sensitivity into mechanically strong nanoclay composite hydrogels based on N -isopropylacrylamideJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2008Siddharthya K. Mujumdar Abstract pH-sensitive nanoclay composite hydrogels based on N -isopropylacrylamide (NIPA) were synthesized by copolymerization with cationic and anionic comonomers. Laponite nanoclay particles served as multifunctional crosslinkers, producing hydrogels with exceptionally high mechanical strengths, as measured by elongation at break. Cationic copolymer gels based on NIPA and dimethylaminoethylmethacrylate were prepared by aqueous free radical polymerization, adopting a procedure reported by Haraguchi (Adv Mater 2002, 14, 1120,1124). Without modification, this technique failed to produce anionic copolymer gels of NIPA and methacrylic acid (MAA), due to flocculation of clay particles. Three methods were conceived to incorporate acidic MAA into nanoclay hydrogels. First, NIPA was copolymerized with sodium methacrylate under dilute conditions, producing hydrogels with good pH-sensitivity but weak mechanical characteristics. Second, NIPA was copolymerized with methyl methacrylate, which was then hydrolyzed to generate acid sidegroups, yielding hydrogels that were much stronger but less pH sensitive. Third, NIPA was copolymerized with MAA following modification of the nanoclay surface with pyrophosphate ions. The resulting hydrogels exhibited both strong pH-sensitivities at 37 °C and excellent tensile properties. Optical transparency changed during polymerization, depending on hydrophobicity of the components. This work increases the diversity and functionality of nanoclay hydrogels, which display certain mechanical advantages over conventionally crosslinked hydrogels. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6630,6640, 2008 [source] Cellular Evaluation of Synthesized Insulin/Transferrin Bioconjugates for Oral Insulin Delivery Using Intelligent Complexation HydrogelsMACROMOLECULAR BIOSCIENCE, Issue 3 2010Justin P. Shofner Abstract Insulin transport across the epithelial cell layer in the small intestine was studied using insulin/transferrin conjugates with and without the presence of P(MAA -g- EG) microparticles in contact with a co-culture of Caco-2/HT29-MTX cells. The insulin/transferrin conjugate was shown to increase transport relative to pure insulin by a factor of 7, achieving an apparent permeability of 37,×,109,cm,·,s,1. The presence of P(MAA- g -EG) microparticles increased conjugate transport by a factor of 14 times relative to insulin, achieving an apparent permeability of 72.8,×,109,cm,·,s,1. The presence of the microparticles in solution was found to improve conjugate transport by nearly 100% with little to no change in cell monolayer integrity. [source] Studies on Preparation and Fluorescent Properties of a Novel Photo-Sensitive Nanoparticle Composed of Europium Ion and Cinnamic Acid DerivativeMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 23 2009Dongjian Shi Abstract A novel fluorescent and photo-sensitive nanoparticle was self-assembled from an europium-based random copolymer, europium coordinated poly(methylacrylic acid)- co -poly(cinnamyl acrylate) (PMCFA-Eu3+), which was synthesized from methylacrylic acid (MAA), and Eu3+ -cinnamyl acrylate derivative (CFA) by radical polymerization. DLS and TEM results indicated the formation of spherical nanoparticles with 120,nm in diameter. The PMCFA-Eu3+ complex showed stronger fluorescence than Eu3+, indicating the effective energy transferred from the ligand to Eu3+. Moreover, the photo-crosslinking of the cinnamate groups induced a decrease in the diameter and an increase in the fluorescent properties of the PMCFA-Eu3+ nanoparticles. This functional nanoparticle might be useful as a carrier and a fluorescence probe in biomedical and fluorescent fields. [source] Cloud-Point Pressure Curves of Ethene/Poly[ethylene- co -((meth)acrylic acid)] MixturesMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 4 2003Michael Buback Abstract Ethene-methacrylic acid (MAA) and ethene-acrylic acid (AA) copolymers of narrow polydispersity and high chemical homogeneity have been synthesized at acid unit copolymer contents up to 9 mol-% within a continuously operated stirred tank reactor at overall monomer conversions of about 2%. Cloud-point pressures (CPPs) of mixtures of 3 wt.-% copolymer in ethene (E) have been measured in an optical high-pressure cell at pressures and temperatures up to 3,000 bar and 260,°C, respectively. The CPP weakly increases with acid copolymer content up to about 3.5 mol-%. Toward higher acid contents, the CPP is strongly enhanced, in particular at the lower edge of the experimental temperature range at around 200,°C. This increase in CPP is more pronounced for the AA than for the MAA systems. The data suggest that hydrogen-bonding interactions are operative in the pressurized E/poly(E- co -(M)AA) mixtures at temperatures of 260,°C and perhaps even above. E-AA and E-MAA copolymers with acid contents of about 5.6 mol-% have also been completely methyl-esterified to yield the associated methyl esters. The CPPs of the resulting E-methyl acrylate and E-methyl methacrylate copolymers in mixtures with E are significantly below the CPPs of the corresponding E/poly(E- co -(M)AA) systems. Cloud-point pressure vs temperature curves for several E/poly(E- co -methacrylic acid) systems. The subscripts denote copolymer content in mol-%. A cloud-point pressure curve for E/polyethylene (PE) is included for comparison. [source] Effect of Surface Modification on the Synthesis of Pore-Filling Polymeric Monoliths in Microfiltration Membranes Made from Poly(propylene) and Poly(ethylene terephthalate)MACROMOLECULAR MATERIALS & ENGINEERING, Issue 3 2007Abdus Salam Abstract The effect of pre-modification on the interaction of macroporous substrates (membranes) with mainly micro- and mesoporous polymer monoliths has been studied. Bulk, porous polymer monoliths were synthesized to optimize the synthesis conditions and their pore morphology, and the data were used as benchmark for this study. Pre-modification of the entire pore surface of PP microfiltration membranes and PET track-etched membranes by UV-initiated grafting with PEGMA was performed using well-established methods, including coating with the photo-initiator, benzophenone. Subsequently, these membranes were functionalized by filling the pores with porous polymer monoliths from MAA and EDMA and compared with membranes that had been functionalized without the pre-modification step. The materials were characterized mainly by the degree of grafting, SEM and by the gas-adsorption-isotherm method. The DG values, after composite-membrane preparation under identical conditions, were not influenced by the pre-modification. However, it could be clearly seen from the SEM images that the pre-modification step prevents the formation of voids at the monolith-membrane pore interface. Larger specific surface area and pore volume values for composite membranes, prepared after pre-modification, fully support the SEM results. Especially large differences in pore structure between the two different composite membranes were found in the mesopore range. The results of this study indicate that it is possible to prepare porous, composite membranes where the trans-membrane transport is exclusively controlled by the pore and surface structure of a functional polymeric monolith, for example, made from a molecularly-imprinted polymer. [source] Aliphatic Ketones as Photoinitiators for PhotograftingMACROMOLECULAR RAPID COMMUNICATIONS, Issue 13 2004Huiliang Wang Abstract Summary: The photografting of methacrylic acid (MAA) onto high-density polyethylene (HDPE) initiated by butanone, pentan-3-one, and heptan-3-one is presented. These aliphatic ketones can act as photoinitiators for photografting when they are a component of a suitable solvent mixture with water and ethanol. It is possible that the photoinitiation effect of the aliphatic ketone is induced by the hydrogen bond formed between it and water. The grafting of 2 M MAA in different ketone/water/ethanol (30/30/40) solvents. [source] Developing tools for the safety specification in risk management plans: lessons learned from a pilot project,PHARMACOEPIDEMIOLOGY AND DRUG SAFETY, Issue 5 2008Andrew J. P. Cooper BSc Abstract Purpose Following the adoption of the ICH E2E guideline, risk management plans (RMP) defining the cumulative safety experience and identifying limitations in safety information are now required for marketing authorisation applications (MAA). A collaborative research project was conducted to gain experience with tools for presenting and evaluating data in the safety specification. This paper presents those tools found to be useful and the lessons learned from their use. Methods Archive data from a successful MAA were utilised. Methods were assessed for demonstrating the extent of clinical safety experience, evaluating the sensitivity of the clinical trial data to detect treatment differences and identifying safety signals from adverse event and laboratory data to define the extent of safety knowledge with the drug. Results The extent of clinical safety experience was demonstrated by plots of patient exposure over time. Adverse event data were presented using dot plots, which display the percentages of patients with the events of interest, the odds ratio, and 95% confidence interval. Power and confidence interval plots were utilised for evaluating the sensitivity of the clinical database to detect treatment differences. Box and whisker plots were used to display laboratory data. Conclusions This project enabled us to identify new evidence-based methods for presenting and evaluating clinical safety data. These methods represent an advance in the way safety data from clinical trials can be analysed and presented. This project emphasises the importance of early and comprehensive planning of the safety package, including evaluation of the use of epidemiology data. Copyright © 2008 John Wiley & Sons, Ltd. [source] Sulfur Deficiency Changes Mycosporine-like Amino Acid (MAA) Composition of Anabaena variabilis PCC 7937: A Possible Role of Sulfur in MAA BioconversionPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2010Shailendra P. Singh In the present investigation we show for the first time that bioconversion of a primary mycosporine-like amino acid (MAA) into a secondary MAA is regulated by sulfur deficiency in the cyanobacterium Anabaena variabilis PCC 7937. This cyanobacterium synthesizes the primary MAA shinorine (RT = 2.2 min, ,max = 334 nm) under normal conditions (PAR + UV-A + UV-B); however, under sulfur deficiency, a secondary MAA palythine-serine (RT = 3.9 min, ,max = 320 nm) appears. Addition of methionine to sulfur-deficient cultures resulted in the disappearance of palythine-serine, suggesting the role of primary MAAs under sulfur deficiency in recycling of methionine by donating the methyl group from the glycine subunit of shinorine to tetrahydrofolate to regenerate the methionine from homocysteine. This is also the first report for the synthesis of palythine-serine by cyanobacteria which has so far been reported only from corals. Addition of methionine also affected the conversion of mycosporine-glycine into shinorine, consequently, resulted in the appearance of mycosporine-glycine (RT = 3.6 min, ,max = 310 nm). Our results also suggest that palythine-serine is synthesized from shinorine. Based on these results we propose that glycine decarboxylase is the potential enzyme that catalyzes the bioconversion of shinorine to palythine-serine by decarboxylation and demethylation of the glycine unit of shinorine. [source] Effects of salinity and ultraviolet radiation on the concentration of mycosporine-like amino acids in various isolates of the benthic cyanobacterium Microcoleus chthonoplastesPHYCOLOGICAL RESEARCH, Issue 2 2002Ulf Karsten SUMMARY The effects of salinity and ultraviolet B (UV-B) treatment on the intracellular mycosporine-like amino acid (MAA) concentration in three isolates of the benthic cyanobacterium Microcoleus chthonoplastes from the Baltic Sea (WIS), Spain (EBD) and Australia (TOW) were compared. All strains contained shinorine and, in addition, both EBD and TOW exhibited the unknown MAA-332, and WIS exhibited the unknown MAA-346. Salinity treatment led to MAA accumulation in TOW and WIS, but not in EBD. Whereas UV-B exposure was accompanied by a strong increase in MAA in EBD and TOW, WIS did not survive the treatment. All data indicate isolate-specific MAA accumulation patterns under different environmental conditions and can be explained by ecotypic differentiation. A double function of MAAs as organic osmolytes and photoprotect-ants seems possible. [source] Analysis of the swelling dynamics of crosslinked P(N -iPAAm- co -MAA) copolymers, the corresponding homopolymers and their interpenetrating networks.POLYMER INTERNATIONAL, Issue 6 2003Kinetics of water penetration into the gel above the pKaof MAA comonomeric units Abstract The effect of composition on the swelling kinetics of a series of crosslinked poly(N -isopropylacrylamide)s [P(N -iPAAm)] and poly(methacrylic acid)s [P(MAA)], their statistical copolymers P(N -iPAAm- co -MAA), and some sequential interpenetrating networks (IPNs) has been studied at pHs above the pKa of MAA comonomeric units. The swelling process of the hydrogels upon immersion in buffer solutions was monitored by the weight change as a function of time. First-order kinetics apply better than second-order kinetics which fail, especially for predicting swelling equilibrium values. However, hydrogels presenting hydrogen bonding between MAA and N -iPAAm units do not obey either first-order or second-order kinetics. The high n values found indicate that the swelling process is mostly controlled by polymer relaxation. Copyright © 2003 Society of Chemical Industry [source] Effects of hydrophilic monomer types on poly(styrene-acrylate)/montmorillonite nanocomposites made by in-site emulsion polymerization,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 6 2009Fa-Ai Zhang Abstract Organic modified montmorillonite (OMMT) was made of pristine montmorillonite (MMT) treated with cetyl trimethylammonium bromide (CTAB). Two kinds of nanocomposites, poly(styrene-acrylate)/MMT (P(S-A)/MMT) and poly (styrene-acrylate)/OMMT (P(S-A)/OMMT) were prepared from styrene (St), hydrophilic acrylate monomer, and MMT (or OMMT) by in-site emulsion polymerization. Effects of different monomers, , -hydroxyethyl methacrylate (HEMA), acrylic acid (AA), methacryclic acid (MAA) on the thermal stability of the two nanocomposites were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). The structures of the nanocomposites were characterized by infrared spectroscopy (IR) and X-ray diffraction (XRD). The morphology of the nanocomposite was observed by transmission electron microscope (TEM). The results showed that the thermal stabilities of the two composites were enhanced by the addition of HEMA, AA, or MAA. The P(S-A)/OMMT nanocomposite showed higher thermal stability than that of the P(S-A)/MMT nanocomposite. In particular, HEMA improved the thermal stability of the P(S-A)/OMMT nanocomposite, which is more efficient than methacrylic acid (MA) and AA. Copyright © 2009 John Wiley & Sons, Ltd. [source] Synthesis and characterization of dual-responsive micrometer-sized core-shell composite polymer particlesPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 3 2008M. Ashraful Alam Abstract Dual-responsive micrometer-sized core-shell composite polymer particles were prepared by dispersion polymerization followed by seeded copolymerization. Polystyrene (PS) particles prepared by dispersion polymerization were used as core particles. N-isopropyl acrylamide (NIPAM) and methacrylic acid (MAA) were used to induce dual-responsive that is thermo- and pH-responsive properties in the shell layer of composite polymer particles, prepared by seeded copolymerization with PS core particles. Temperature- and pH-dependent adsorption behaviors of some macromolecules on composite polymer particles indicate that produced composite polymer particles exhibit dual-responsive surface properties. Copyright © 2007 John Wiley & Sons, Ltd. [source] | |||||||||||||||||||