Showing papers on "Acrylic acid published in 2011"

Different EDC/NHS activation mechanisms between PAA and PMAA brushes and the following amidation reactions.

Abstract: Infrared spectroscopy was applied to investigate the well-known EDC/NHS (N-ethyl-N'-(3-(dimethylamino)propyl)carbodiimide/N-hydroxysuccinimide) activation details of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) brushes grafted on porous silicon. Succinimidyl ester (NHS-ester) is generally believed to be the dominant intermediate product, conveniently used to immobilize biomolecules containing free primary amino groups via amide linkage. To our surprise, the infrared spectral details revealed that the EDC/NHS activation of PMAA generated anhydride (estimated at around 76% yield and 70% composition), but not NHS-ester (around 5% yield and 11% composition) under the well-documented reaction conditions, as the predominant intermediate product. In contrast, EDC/NHS activation of PAA still follows the general rule, i.e., the expected NHS-ester is the dominant intermediate product (around 45% yield and 57% composition), anhydride the side product (40% yield and 28% composition), under the optimum reaction conditions. The following amidation on PAA-based NHS-esters with a model amine-containing compound, L-leucine methyl ester, generated approximately 70% amides and 30% carboxylates. In contrast, amidation of PAA- or PMAA-based anhydrides with L-leucine methyl ester only produced less than 30% amides but more than 70% carboxylates. The above reaction yields and percentage compositions were estimated by fitting the carbonyl stretching region with 5 possible species, NHS-ester, anhydride, N-acylurea, unreacted acid, unhydrolyzed tert-butyl ester, and using the Beer-Lambert law. The different surface chemistry mechanisms will bring significant effects on the performance of surface chemistry-derived devices such as biochips, biosensors, and biomaterials.

Novel Amphiphilic Multi-Arm, Star-Like Block Copolymers as Unimolecular Micelles

Abstract: A series of novel amphiphilic multiarm, star-like block copolymers, poly(acrylic acid)-b-polystyrene (PAA-b-PS) based on β-cyclodextrin (β-CD) with well-defined molecular architectures, molecular weight, and ratio of two dissimilar blocks were prepared by sequential atom transfer radical polymerization (ATRP). β-CD with 21 hydroxyl groups was esterified by the reaction of its hydroxyl end groups with 2-bromoisobutyryl bromide, producing star-like heptakis[2,3,6-tri-O-(2-bromo-2-methylpropionyl]-β-cyclodextrin) (denoted 21-Br-β-CD). Subsequently, 21-Br-β-CD was utilized to initiate sequential ATRP of tert-butyl acrylate (tBA) and styrene (St). A series of 21-arm, star-like diblock copolymers, poly(tert-butyl acrylate)-b-polystyrene (PtBA-b-PS) were thus obtained. Finally, the ester groups of tBA in star-like PtBA-b-PS were selectively hydrolyzed by trifluoroacetic acid (TFA), thereby yielding amphiphilic 21-arm, star-like diblock copolymer PAA-b-PS with narrow molecular weight distribution (polydispersity ...

Xylan-rich Hemicelluloses-graft-Acrylic Acid Ionic Hydrogels with Rapid Responses to pH, Salt, and Organic Solvents

Abstract: Exploitation of biomaterials derived from renewable resources is an important approach to address environmental and resource problems in the world today. In this paper, novel ionic hydrogels based on xylan-rich hemicelluloses were prepared by free radical graft copolymerization of acrylic acid (AA) and xylan-rich hemicelluloses (XH) by using N,N-methylene-bis(acrylamide) (MBA) as cross-linker and ammonium persulfate/N,N,N',N'-tetramethylethylenediamine (APS/TMEDA) as redox initiator system. The network characteristics of the ionic hydrogels were investigated by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM), as well as by determination of mechanical properties, swelling, and stimuli responses to pH, salts, and organic solvents. The results showed that an increase in the MBA/XH or AA/XH ratio resulted in higher cross-linking density of the network and thus decreased the swelling ratio. Expansion of the network hydrogels took place at high pH, whereas shrinkage occurred at low pH or in salt solutions as well as in organic solvents. The ionic hydrogels had high water adsorption capacity and showed rapid and multiple responses to pH, ions, and organic solvents, which may allow their use in several areas such as adsorption, separation, and drug release systems.

Effect of extended polymer chains on properties of transparent graphene nanosheets conductive film

Abstract: This study examined the intercalation reaction of graphite oxide (GO) with poly(acryl amide)/poly(acrylic acid) (PMA) as a method to control the spacing between GOs. The interlayer spacing of GO was increased from 0.80 to 1.21 nm by grafting PMA on the GO surface. To fabricate transparent conductive films (TCFs), GOs must be reduced to graphene nanosheets (GNS) by a two-step chemical reduction with increased conductivity. The intercalated polymer chains of poly(acrylic acid) between GNS were extended as the carboxylic acid groups were deprotonated by the Na+ ions of NaBH4 on reduction, which efficiently inhibits GNS aggregation and restacking. The Na+ bonding on the polymer chains also facilitates electron transfer between the layers, yielding lower surface electrical resistance at the same GNS film thickness. The PMA grafted GNS (NE-PMA-GNS) composite films show the lowest sheet resistance of 2.11 × 102 Ω □−1, which is one order of magnitude less than that without grafting polymer (NE-GNS, 1.86 × 103 Ω □−1); moreover, instead of 0.22, the ratio of DC conductivity to optical conductivity (σDC/σOP) was 2.60. The higher σDC/σOP ratio indicates a higher TCFs performance.

Amphiphilic Block Copolymers from a Direct and One‐pot RAFT Synthesis in Water

Abstract: The syntheses of amphiphilic block copolymers are successfully performed in water by chain extension of hydrophilic macromolecules with styrene at 80 °C. The employed strategy is a one-pot procedure in which poly(acrylic acid), poly(methacrylic acid) or poly(methacrylic acid-co-poly(ethylene oxide) methyl ether methacrylate) macroRAFTs are first formed in water using 4-cyano-4-thiothiopropylsulfanyl pentanoic acid (CTPPA) as a chain transfer agent. The resulting macroRAFTs are then directly used without further purification for the RAFT polymerization of styrene in water in the same reactor. This simple and straightforward strategy leads to a very good control of the resulting amphiphilic block copolymers.

Efficient Acrylic Acid Production through Bio Lactic Acid Dehydration over NaY Zeolite Modified by Alkali Phosphates

Abstract: Alkali phosphates-modified NaY zeolites were developed as catalysts for efficient conversion of lactic acid to acrylic acid. The catalytic performance was optimized in terms of the type and loading of alkali phosphates, reaction temperature, liquid hourly space velocity, and lactic acid concentration. A high acrylic acid yield of 58.4% was achieved at 340 °C over 14 wt % Na2HPO4/NaY. The physicochemical properties of the catalysts were investigated by various techniques including NH3-TPD, pyridine adsorption-FTIR, Raman, and MAS 31P NMR. Introduction of alkali phosphates to NaY zeolite results in a decline of surface acidity. The results of FTIR, Raman, and MAS 31P NMR investigations on the fresh and used catalysts suggest that sodium phosphate is largely transformed to sodium lactate during the reaction. The phosphates and the in situ generated sodium lactate function as highly active species for the target reaction.

Wetting Behavior of Oleophobic Polymer Coatings Synthesized from Fluorosurfactant-Macromers

Abstract: Architecturally similar monomers were copolymerized with a water–oil discriminate fluorosurfactant to create hydrophilic–oleophobic coatings. Acrylic acid, hydroxyethyl methacrylate, and methyl methacrylate were used as comonomers with the fluorosurfactant macromer. The homopolymers of the selected comonomers are water-soluble, water-swellable, and water-insoluble, respectively, thus coupling the surfactant monomer in varying concentration within polymers of varying hydrophilicity. Wetting behavior of water and hexadecane were examined as a function of copolymer composition, thus revealing critical structure–property relationships for the surfactant-based system. Acrylic acid copolymers and hydroxyethyl methacrylate copolymers both exhibited a hexadecane contact angle which exceeded the water contact angle. This condition predicted an ability to “self-clean” oil-based foulants. The most oleophobic of the self-cleaning copolymers had an advancing hexadecane contact angle of 73° and an advancing water conta...

2,7-Diaminofluorene-based organic dyes for dye-sensitized solar cells: effect of auxiliary donor on optical and electrochemical properties.

Abstract: New organic dyes containing a diarylaminofluorene unit as an electron donor and cyanoacrylic acid as acceptor and anchoring group in a donor-π-donor-π-acceptor architecture have been synthesized and characterized as sensitizers for nanocrystalline TiO2-based dye-sensitized solar cells. They have shown three major electronic absorptions originating from the π–π* and charge-transfer transitions covering the broad visible range (250–550 nm) in solution. The charge-transfer transition of the dyes exhibited negative solvatochromism, suggesting a polarized ground state. They have also displayed acidochromism in solution owing to the presence of a protonation–deprotonation equilibrium. On comparison with the triphenylamine and carbazole-based parent dyes (E)-2-cyano-3-(4-(diphenylamino)phenyl)acrylic acid and (E)-2-cyano-3-(9-ethyl-9H-carbazol-3-yl)acrylic acid they exhibited longer wavelength absorptions and facile oxidation, indicating the stronger electron-donating ability of the auxiliary chromophores. In ad...

Ethylenediaminetetraacetic acid (EDTA)-controlled synthesis of multicolor lanthanide doped BaYF5 upconversion nanocrystals

Abstract: Here lanthanide-doped tetragonal nanocrystals of BaYF5 with strong near infrared-to-visible multicolor upconversion emissions have been controllably synthesized by a hydrothermal method Opposite to well-established NaYF4 nanocrystals, we found that the sizes of the BaYF5 nanocrystals increase in proportion to that of the molar ratios of EDTA to lanthanide nitrates and decrease as the pH value of the precursor solution increases in presence of EDTA These findings reveal that the nucleation process of BaYF5 nanocrystals is governed by the pH-sensitive chelating ability of EDTA with both Ba2+ and Ln3+ Additionally, it was found that single wavelength laser excitation of 980 nm can induce strong red, green, and blue upconversion emissions in BaYF5 nanocrystals doped with 18%Yb3+/2%Er3+, 18%Yb3+/2%Ho3+, and 18%Yb3+/2%Tm3+, respectively Furthermore, after a facile surface poly(acrylic acid) ligand exchange reaction, such multicolor nanoparticles can be transferred into water and multiple other solvents for applications in biology and materials science

Influence of the stirring speed and CaCl2 concentration on the nano‐object morphologies obtained via RAFT‐mediated aqueous emulsion polymerization in the presence of a water‐soluble macroRAFT agent

Abstract: Aqueous emulsion polymerizations of styrene were performed in the presence of a macromolecular reversible addition-fragmentation chain transfer (RAFT) agent (macroRAFT) composed of acrylic acid (AA) and poly(ethylene oxide) methyl ether acrylate (PEOA), end-capped by a reactive dodecyl trithiocarbonate group (P(AA-co-PEOA)-TTC). The influence of the stirring speed or the presence of different amounts of a divalent salt, CaCl2, were investigated in this polymerization-induced self-assembly process, in which spherical and nonspherical nano-objects were formed upon the synthesis of amphiphilic diblock copolymers in situ. It appeared that the addition of CaCl2 led to the controlled formation of different nano-objects such as spheres, fibers or vesicles, whereas an appropriate stirring speed was required for the formation of nanofibers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Synthesis of Acrylic-Polyurethane Hybrid Latexes by Miniemulsion Polymerization and Their Pressure-Sensitive Adhesive Applications

Abstract: The successful incorporation of a NCO-terminated polyurethane (PU) prepolymer in a hybrid miniemulsion is described with the purpose to develop waterborne, high solids, acrylic−PU hybrid nanoparticles to be used in pressure-sensitive adhesive (PSA) applications. To ensure efficient chemical incorporation of the reactive PU into the hybrid latex particles, the NCO moieties were reacted with 2-hydroxyethyl methacrylate (HEMA). The NCO−HEMA coupling reaction was thoroughly studied by conductimetry in order to control the extent of HEMA incorporation into the PU chains. The resulting HEMA-end-capped prepolymers were chain extended in situ with Bisphenol A (BPA) and polymerized with n-butyl acrylate, methyl methacrylate, and acrylic acid in the presence of small amounts of a chain transfer agent to form PU/acrylic particles. The amount of chain transfer agent, the ratio between HEMA and BPA, and the amount of PU were varied step by step to study their influence on the final film properties. The miniemulsions a...

Preparation of Imprinted Polymers at Surface of Magnetic Nanoparticles for the Selective Extraction of Tadalafil from Medicines

Abstract: In this paper, highly selective core–shell molecularly imprinted polymers (MIPs) of tadalafil on the surface of magnetic nanoparticles (MNPs) were prepared. Three widely used functional monomers 2-(trifluoromethyl) acrylic acid (TFMAA), acrylic acid (AA), and methacrylic acid (MAA) were compared theoretically as the candidates for MIP preparation. MIP-coated magnetic nanoparticles (MIP-coated MNPs) showed large adsorption capacity, high recognition ability, and fast binding kinetics for tadalafil. Furthermore, because of the good magnetic properties, MIP-coated MNPs can achieve rapid and efficient separation with an external magnetic field simply. The resulting MIP-coated MNPs were used as dispersive solid-phase extraction (DSPE) materials coupled with HPLC-UV for the selective extraction and detection of tadalafil from medicines (herbal sexual health products). Encouraging results were obtained. The amounts of tadalafil that were detected from the herbal sexual health product was 43.46 nmol g–1, and the ...

Synthesis of Molecularly Imprinted Polymers for Amino Acid Derivates by Using Different Functional Monomers

Abstract: Fmoc-3-nitrotyrosine (Fmoc-3-NT) molecularly imprinted polymers (MIPs) were synthesized to understand the influence of several functional monomers on the efficiency of the molecular imprinting process. Acidic, neutral and basic functional monomers, such as acrylic acid (AA), methacrylic acid (MAA), methacrylamide (MAM), 2-vinylpyridine (2-VP), 4-vinylpyridine (4-VP), have been used to synthesize five different polymers. In this study, the MIPs were tested in batch experiments by UV-visible spectroscopy in order to evaluate their binding properties. The MIP prepared with 2-VP exhibited the highest binding affinity for Fmoc-3NT, for which Scatchard analysis the highest association constant (2.49 × 104 M−1) was obtained. Furthermore, titration experiments of Fmoc-3NT into acetonitrile solutions of 2-VP revealed a stronger bond to the template, such that a total interaction is observed. Non-imprinted polymers as control were prepared and showed no binding affinities for Fmoc-3NT. The results are indicative of the importance of ionic bonds formed between the –OH residues of the template molecule and the pyridinyl groups of the polymer matrix. In conclusion, 2-VP assists to create a cavity which allows better access to the analytes.

Method for producing water absorbent polyacrylic acid (salt) resin powder, and water absorbent polyacrylic acid (salt) resin powder

Abstract: An object of the present invention is to provide a method for producing water absorbent resin powder in which permeability potential (SFC) is improved while a water absorbing rate (FSR) is being kept. The method is a method for producing water absorbent polyacrylic acid (salt) resin powder including the steps of: (i) polymerizing an acrylic acid (salt) monomer aqueous solution; (ii) during or after the step of (i), performing gel grinding of a hydrogel crosslinked polymer obtained by the polymerization, wherein the hydrogel crosslinked polymer has resin solid content of 10 wt % to 80 wt %, and the gel grinding is carried out with gel grinding energy (GGE) of 18 [J/g] to 60 [J/g]; (iii) drying a particulate hydrogel crosslinked polymer obtained by the gel grinding, wherein the drying is performed at 150° C. to 250° C.; and (iv) carrying out a surface treatment to the particulate hydrogel crosslinked polymer thus dried.

Benefits and drawbacks of zinc in glass ionomer bone cements

Abstract: Glass polyalkenoate (ionomer) cements (GPCs) based on poly(acrylic acid) and fluoro-alumino-silicate glasses are successfully used in a variety of orthopaedic and dental applications; however, they release small amounts of aluminium, which is a neurotoxin and inhibits bone mineralization in vivo. Therefore there has been significant interest in developing aluminium-free glasses containing zinc for forming GPCs because zinc can play a similar structural role in the glass, allowing for glass degradation and subsequent cement setting, and is reported to have beneficial effects on bone formation. We created zinc-containing GPCs and characterized their mechanical properties and biocompatibility. Zinc-containing cements showed adhesion to bone close to 1 MPa, which was significantly greater than that of zinc-free cements (<0.05 MPa) and other currently approved biological adhesives. However, zinc-containing cements produced significantly lower metabolic activity in mouse osteoblasts exposed to cell culture medium conditioned with the cements than controls. Results show that although low levels of zinc may be beneficial to cells, zinc concentrations of 400 µM Zn(2+) or more resulted in cell death. In summary, we demonstrate that while zinc-containing GPCs possess excellent mechanical properties, they fail basic biocompatibility tests, produce an acute cytotoxic response in vitro, which may preclude their use in vivo.

Tuning of Lower Critical Solution Temperature (LCST) of Poly(N-Isopropylacrylamide-co-Acrylic acid) Hydrogels

Abstract: Temperature-responsive hydrogel with a lower critical solution temperature (LCST) close to human body temperature was prepared. Crosslinked N-isopropylacrylamide (NIPAAm) and acrylic acid (AAc) copolymer networks were synthesized at various monomer ratios in the presence of ammonium persulfate (APS), N,N′-methylenebisacrylamide (NMBA) and N,N,N′,N′-tetramethylethylenediamine (TEMED) via a redox polymerization method. The resulting hydrogels possessed thermo- and pH-responsive characteristics. They were characterized in terms of swelling ratio, volume change, water uptake and diffusivity, water vapor uptake and diffusivity, and phase transition temperature. The water liquid and vapor diffusion coefficients for all the synthesized hydrogels were higher than the literature data, implying higher rates for drug release. The LCST of the hydrogel increased with higher AAc content in the copolymer. The gel containing 1.8% AAc exhibited an LCST similar to human body temperature, demonstrating a potential use in dr...

pH-induced changes in the fabrication of multilayers of poly(acrylic acid) and chitosan: fabrication, properties, and tests as a drug storage and delivery system.

Abstract: Multilayers of poly(acrylic acid), PAA, and chitosan, CHI, have been built by the layer-by-layer (LbL) method from aqueous solutions at different pH values and analyzed by the dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The results showed that under all of the assembly conditions considered the growth of the films is nonlinear. The thickness of the PAA layers increases as the pH of the assembling solutions decreases, whereas the adsorption of CHI is almost unaffected by the pH conditions. The comparison of the thickness obtained by D-QCM and by ellipsometry has allowed us to calculate the water content of the films, showing that the multilayers are highly hydrated, with an average water content higher than 20%. The analysis of D-QCM data has provided high-frequency values of the complex shear modulus that are in the megapascal range and shows a transition from mainly viscous to mainly elastic behavior for the added PAA layers, depending on the pH. The monomer surface density in each ...