Cross‐Linked Multilayers of Poly(vinyl amine) as a Single Component and Their Interaction with Proteins

Novel multilayer thin films that consist solely of cross‐linked single component layers are generated by a selective cross‐linking of the poly(vinyl amine) (PVAm) layers in [PVAm/poly(acrylic acid) (PAA)]_n thin films constructed either on silica particles or silicon wafers, followed by the removal of PAA. The surface topography of the (PVAm)_n multilayer thin films, before and after the adsorption of human serum albumin (HSA), has been studied by atomic force microscopy on the freeze‐dried films. The decrease of the average roughness of the film after the adsorption of HSA showed the protein was adsorbed into the (PVAm)_n film making these films potential reservoirs for proteins.

     

Enhanced CO2 Adsorption over Polymeric Amines Supported on Heteroatom‐Incorporated SBA‐15 Silica: Impact of Heteroatom Type and Loading on Sorbent Structure and Adsorption Performance

Silica supported amine materials are promising compositions that can be used to effectively remove CO₂ from large stationary sources, such as flue gas generated from coal‐fired power plants (ca. 10 % CO₂) and potentially from ambient air (ca. 400 ppm CO₂). The CO₂ adsorption characteristics of prototypical poly(ethyleneimine)–silica composite adsorbents can be significantly enhanced by altering the acid/base properties of the silica support by heteroatom incorporation into the silica matrix. In this study, an array of poly(ethyleneimine)‐impregnated mesoporous silica SBA‐15 materials containing heteroatoms (Al, Ti, Zr, and Ce) in their silica matrices are prepared and examined in adsorption experiments under conditions simulating flue gas (10 % CO₂ in Ar) and ambient air (400 ppm CO₂ in Ar) to assess the effects of heteroatom incorporation on the CO₂ adsorption properties. The structure of the composite adsorbents, including local information concerning the state of the incorporated heteroatoms and the overall surface properties of the silicate supports, are investigated in detail to draw a relationship between the adsorbent structure and CO₂ adsorption/desorption performance. The CO₂ adsorption/desorption kinetics are assessed by thermogravimetric analysis and in situ FT‐IR measurements. These combined results, coupled with data on adsorbent regenerability, demonstrate a stabilizing effect of the heteroatoms on the poly(ethyleneimine), enhancing adsorbent capacity, adsorption kinetics, regenerability, and stability of the supported aminopolymers over continued cycling. It is suggested that the CO₂ adsorption performance of silica–aminopolymer composites may be further enhanced in the future by more precisely tuning the acid/base properties of the support.     

Functional membranes prepared by layer‐by‐layer assembly and its metal ions adsorption property

PVDF/(PEI‐C/PAA)_n functional membranes were prepared by layer‐by‐layer (LbL) assembly, and their heavy metal ions adsorption capability was investigated. The changes in the chemical compositions of membrane surfaces were determined by X‐ray photoelectron spectroscopy (XPS). XPS results show that the surface of the PVDF membrane can be alternatively functionalized by PEI‐C and PAA. The membrane surface hydrophilicity was evaluated through water contact angle measurement. Contact angle results show that the surface hydrophilicity of the membrane surface depends on the outermost deposited layer. Morphological changes of membrane surfaces were observed by scanning electron microscopy (SEM). The water fluxes for these membranes were elevated after modification. The performances of the PVDF/(PEI‐C/PAA)_n membranes on the adsorption of copper ions (Cu²⁺) from aqueous solutions were investigated by inductively coupled plasma (ICP). The results indicate that the PVDF/(PEI‐C/PAA)_n functional membranes show high copper ions adsorption ability. Copyright © 2010 John Wiley & Sons, Ltd.     

Redox Properties of Ferricyanide Ion on Layer‐by‐Layer Thin Film‐Coated Gold Electrodes; Effects of Type of Polycationic Components in the Film

The surface of a gold (Au) electrode was coated with layer‐by‐layer (LbL) thin films composed of poly(vinyl sulfate) (PVS) and different type of poly(amine)s including poly(allylamine) (PAH), poly(ethyleneimine) (PEI) and poly(diallyldimethylammonium chloride) (PDDA) and redox properties of ferricyanide ion ([Fe(CN)₆]^3?) on the LbL film‐coated Au electrodes were studied. The LbL film‐coated electrodes exhibited redox response to [Fe(CN)₆]^3? ion when the outermost surface of the LbL film was covered with the cationic poly(amine)s while virtually no response was observed on the LbL film‐coated electrodes whose outermost surface was covered with PVS due to an electrostatic repulsion between [Fe(CN)₆]^3? ion and the negatively‐charged PVS layer. The redox properties of [Fe(CN)₆]^3? ion on the LbL film‐coated electrodes significantly depended on the type of polycationic materials in the LbL film. The LbL film‐coated electrodes which had been immersed in the [Fe(CN)₆]^3? solution for 15 min exhibited redox response even in a [Fe(CN)₆]^3? ion‐free buffer solution, suggesting that [Fe(CN)₆]^3? ion is confined in the films. In the buffer solution, redox peaks were observed between +0.1 and 0.4 V depending on the type of polycations in the film. Thus, [Fe(CN)₆]^3? ion can be confined in the film and the redox potential is polycation‐dependent.     

Ultrathin pH‐Sensitive Nanoporous Membranes for Superfast Size‐Selective Separation

Stimuli‐responsive nanoporous membranes have attracted increasing interest in various fields due to their abrupt changes of permeation/separation in response to the external environment. Here we report ultrathin pH‐sensitive nanoporous membranes that are easily fabricated by the self‐assembly of poly(acrylic acid) (PAA) in a metal hydroxide nanostrand solution. PAA‐adsorbed nanostrands (2.5–5.0 nm) and PAA‐Cu^II nanogels (2.0–2.5 nm) grow competitively during self‐assembly. The PAA‐adsorbed nanostrands are deposited on a porous support to fabricate ultrathin PAA membranes. The membranes display ultrafast water permeation and good rejection as well as significant pH‐sensitivity. The 28 nm‐thick membrane has a water flux decrease from 3740 to 1350 L m^?1 h^?1 bar^?1 (pH 2.0 to 7.0) with a sharp decrease at pH 5.0. This newly developed pH‐sensitive nanoporous membranes may find a wide range of applications such as controlled release and size‐ and charge‐selective separation.     

Copper(II) chloride and bromide complexes with 2‐methyl‐2H‐tetrazol‐5‐amine: an X‐ray powder diffraction study

The complex catena‐poly[[dibromidocopper(II)]‐bis(μ‐2‐methyl‐2H‐tetrazol‐5‐amine)‐κ²N⁴:N⁵;κ²N⁵:N⁴], [CuBr₂(C₂H₅N₅)₂]_n, (I), and the isotypic chloride complex catena‐poly[[dichloridocopper(II)]‐bis(μ‐2‐methyl‐2H‐tetrazol‐5‐amine)‐κ²N⁴:N⁵;κ²N⁵:N⁴], [CuCl₂(C₂H₅N₅)₂]_n, (II), were investigated by X‐ray powder diffraction at room temperature. The crystal structure of (I) was solved by direct methods, while the Rietveld refinement of (II) started from the atomic coordinates of (I). In both structures, the Cu atoms lie on inversion centres, adopting a distorted octahedral coordination of two halogen atoms, two tetrazole N atoms and two 5‐amine group N atoms. Rather long Cu—N_amine bonds allow consideration of the amine group as semi‐coordinated. The compounds are one‐dimensional coordination polymers, formed as a result of 2‐methyl‐2H‐tetrazol‐5‐amine ligands bridging via a tetrazole N atom and the amine N atom. In the polymeric chains, adjacent Cu atoms are connected by two such bridges.     

Mono‐ and binuclear nickel catalysts for 1‐hexene polymerization

Polymerization of 1‐hexene was carried out using a mononuclear (MN) catalyst and two binuclear (BN₁ and BN₂) α‐diimine Ni‐based catalysts synthesized under controlled conditions. Ethylaluminium sesquichloride (EASC) was used as an efficient activator under various polymerization conditions. The highly active BN₂ catalyst (2372 g poly(1‐hexene) (PH) mmol^?1 cat) in comparison to BN₁ (920 g PH mmol^?1 cat) and the MN catalyst (819 g PH mmol^?1 cat) resulted in the highest viscosity‐average molecular weight (M_v) of polymer. Moreover, the molecular weight distribution (MWD) of PH obtained using BN₂/EASC was slightly broader than those obtained using BN₁ and MN (2.46 for BN₂ versus 2.30 and 1.96 for BN₁ and MN, respectively). These results, along with the highest extent of chain walking for BN₂, were attributed to steric, nuclearity and electronic effects of the catalyst structures which could control the catalyst behaviour. Differential scanning calorimetry showed that the glass transition temperatures of polymers were in the range ? 58 to ?81 °C, and broad melting peaks below and above 0 °C were also observed. In addition, longer α‐olefins (1‐octene and 1‐decene) were polymerized and characterized, for which higher yield, conversion and molecular weight were observed with a narrower MWD. The polymerization parameters such as polymerization time and polymerization temperature showed a significant influence on the productivity of the catalysts and M_v of samples.     

Three‐Dimensional Ultralarge‐Pore Ia3d Mesoporous Silica with Various Pore Diameters and Their Application in Biomolecule Immobilization

Highly ordered mesoporous three‐dimensional Ia3d silica (KIT‐6) with different pore diameters has been synthesized by using pluronic P123 as surfactant template and n‐butanol as cosolvent at different synthesis temperatures in a highly acidic medium. The materials were characterized by XRD and N₂ adsorption. The synthesis temperature plays a significant role in controlling the pore diameter, surface area, and pore volume of the materials. The material prepared at 150 °C, KIT‐6‐150, has a large pore diameter (11.3 nm) and a high specific pore volume (1.53 cm³ g^?1). We also demonstrate immobilization of lysozyme, which is a stable and hard protein, on KIT‐6 materials with different pore diameters. The amount of lysozyme adsorbed on large‐pore KIT‐6 is extremely large (57.2 μmol g^?1) and is much higher than that observed for mesoporous silicas MCM‐41, SBA‐15, and KIT‐5, mesoporous carbons, and carbon nanocages. The effect of various parameters such as buffer concentration, adsorption temperature, concentration of the lysozyme, and the textural parameter of the adsorbent on the lysozyme adsorption capacity of KIT‐6 was studied. The amount adsorbed mainly depends on solution pH, ionic strength, adsorption temperature, and pore volume and pore diameter of the adsorbent. The mechanism of adsorption on KIT‐6 under different adsorption conditions is discussed. In addition, the structural stability of lysozyme molecules and the KIT‐6 adsorbent before and after adsorption were investigated by XRD, nitrogen adsorption, and FTIR spectroscopy.     

Poly(L‐Glutamic Acid)‐Drug Conjugates for Chemo‐ and Photodynamic Combination Therapy

Despite the polymeric vascular disrupting agent (poly(_L‐glutamic acid)‐graft‐methoxy poly(ethylene glycol)/combretastatin A4) nanoparticles can efficiently inhibit cancer growth, their further application is still a challenge owing to the tumor recurrence and metastasis after treatment. In this study, two poly(_L‐glutamic acid)‐drug conjugates for chemo‐and photodynamic combination therapy are fabricated. PLG‐g‐mPEG‐CA4 nanoparticles are prepared by combretastatin A4 (CA4) and poly(_L‐glutamic acid)‐graft‐methoxy poly(ethylene glycol) (PLG‐g‐mPEG) using the Yamaguchi esterification reaction. PLG‐g‐mPEG‐TPP (TPP: 5, 10, 15, 20‐tetraphenylporphyrin) nanoparticles are constructed using PLG‐g‐mPEG and amine porphyrin through condensation reaction between carboxyl group of PLG‐g‐mPEG and amino group of porphyrin. The results showed that PLG‐g‐mPEG‐CA4 nanoparticles have good antitumor ability. PLG‐g‐mPEG‐TPP nanoparticles can produce singlet oxygen under the laser irradiation. Moreover, the combined therapy of PLG‐g‐mPEG‐CA4 and PLG‐g‐mPEG‐TPP nanoparticles has higher antitumor effect than the single chemotherapy or the single photodynamic therapy in vitro. The combination of CA4 nondrug and photodynamic therapy provides a new insight for enhancing the tumor therapeutic effect with vascular disrupting agents and other therapy.     

Novel synthesis of N‐substituted polyacrylamides: Derivatization of poly(acrylic acid) with amines using a triazine‐based condensing reagent

Poly(acrylic acid) (PAA) was derivatized through the reaction of its pendant carboxylic acid (CO₂H) groups with a wide range of amine‐terminated molecules. These molecules contained alkyl, hydroxyl, sulfonic acid, or perfluoroalkyl groups. N‐substitution of PAA was carried out by the simple addition of 4‐(4,6‐dimethoxy‐1,3,5‐triazin‐2‐yl)‐4‐methylmorpholinium chloride (DMTMM), a triazine‐based condensing reagent, to a mixture of PAA and amine‐terminated molecules. From proton nuclear magnetic resonance and infrared spectroscopy, it was confirmed that these functional molecules were introduced into the PAA side chain via amide bonds. By the alteration of the synthetic conditions, functional side‐chain contents of greater than 95% were achieved for aqueous reactions with taurine, ethanol amine, and butyl amine. Side‐chain conversion was limited to ≤80% for reactions with perfluoroalkyl amines in methanol. Thus, DMTMM is an attractive replacement for carbodiimide condensing reagents such as 1,3‐dicyclohexylcarbodiimide and 1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 126–136, 2006     

Influence of Halogen Substitution in the Ligand Sphere on the Antitumor and Antibacterial Activity of Half‐sandwich Ruthenium(II) Complexes [RuX(η6‐arene)(C5H4N‐2‐CH=N‐Ar)]+

New complexes [(η⁶‐p‐cymene)Ru(C₅H₄N‐2‐CH=N–Ar)X]PF₆ [X = Br ( 1 ), I ( 2 ); Ar = 4‐fluorophenyl ( a ), 4‐chlorophenyl ( b ), 4‐bromophenyl ( c ), 4‐iodophenyl ( d ), 2,5‐dichlorophenyl ( e )] were prepared, as well as 3a – 3e (X = Cl) and the new complexes [(η⁶‐arene)RuCl(N‐N)]PF₆ (arene = C₆H₅OCH₂CH₂OH, N‐N = 2,2′‐bipyridine ( 4 ), 2,6‐(dimethylphenyl)‐pyridin‐2‐yl‐methylene amine ( 5 ), 2,6‐(diisopropylphenyl)‐pyridin‐2‐yl‐methylene amine ( 6 ); arene = p‐cymene, N‐N = 4‐(aminophenyl)‐pyridin‐2‐yl‐methylene amine ( 7 )]. X‐ray diffraction studies were performed for 1a , 1b , 1c , 1d , 2b , 5 , and 7 . Cytotoxicities of 1a – 1d and 2 were established versus human cancer cells epithelial colorectal adenocarcinoma (Caco‐2) (IC₅₀: 35.8–631.0 μM), breast adenocarcinoma (MCF7) (IC₅₀: 36.3–128.8.0 μM), and hepatocellular carcinoma (HepG2) (IC₅₀: 60.6–439.8 μM), 3a – 3e were tested against HepG2 and Caco‐2, and 4 – 7 were tested against Caco‐2. 1 – 7 were tested against non‐cancerous human epithelial kidney cells. 1 and 2 were more selective towards tumor cells than the anticancer drug 5‐fluorouracil (5‐FU), but 3a – 3e (X = Cl) were not selective. 1 and 2 had good activity against MCF7, some with lower IC₅₀ than 5‐FU. Complexes with X = Br or I had moderate activity against Caco‐2 and HepG2, but those with Cl were inactive. Antibacterial activities of 1a , 2b , 3a , and 7 were tested against antibacterial susceptible and resistant Gram‐negative and ‐positive bacteria. 1a , 2b , and 3a showed activity against methicillin‐resistant S. aureus (MIC = 31–2000 μg · mL^–1).     

Three‐component polyaddition of diamines,carbon disulfide,and diacrylates in water

The three‐component polyaddition of diamines, carbon disulfide (CS₂), and diacrylates in water was successfully achieved without the use of a surfactant or catalyst. Appropriate reaction conditions (i.e., reaction temperature, reaction time, and CS₂ feed) enabled the polyaddition of 1,3‐di‐4‐piperidylpropane ( 1a ), CS₂, and 1,6‐hexanediol diacrylate ( 2a ) to afford the corresponding poly(dithiourethane‐amine) containing 83% of dithiourethane units in 84% yield. Polyaddition of other monomers also proceeded under the optimum conditions to afford various poly(dithiourethane‐amine)s. Unsuccessful results for polyaddition in organic solvents such as toluene, tetrahydrofuran, and N,N‐dimethylformamide revealed that the polyaddition is accelerated in water. The obtained poly(dithiourethane‐amine)s adsorbed Au (III) efficiently under acidic conditions, due to the strong interaction of the thiocarbonyl sulfur in the dithiourethane unit with Au (III). The poly(dithiourethane‐amine)s also showed selective adsorption for Au (III) from a mixture of metal ions [Au (III), Fe (III), Mn (II), and Zn (II)], which indicates their potential utilization for the collection of gold. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 845–851, 2010     

Well‐dispersed N‐heterocyclic carbene–palladium complex anchored onto poly(acrylic acid)/poly(vinyl alcohol) nanofibers: Novel,superior and ecofriendly nanocatalyst for the Suzuki–Miyaura cross‐coupling reaction

Polymeric nanocomposite@Pd is one of the crown jewels for the catalysis of cross‐coupling reactions. This Pd nanocomposite on various polymeric supports has been well established to catalyze cross‐coupling reactions, but its preparation supported on the surface of nanofibers has been largely overlooked. Herein, we report the preparation of a poly(acrylic acid) (PAA)/poly(vinyl alcohol) (PVA) nanofiber‐supported N‐heterocyclic carbene–Pd complex. The first step involves the preparation of PAA/PVA nanofibers using the electrospinning process. The second step comprises the reaction of water‐soluble poly(ethylene glycol)‐imidazole with modified PAA/PVA nanofibers followed by introduction of PdCl₂ to achieve successfully the desired nanocomposite. The catalytic activity of this nanocomposite was examined in the expeditious synthesis of biaryl compounds using the Suzuki–Miyaura cross‐coupling reaction under mild reaction conditions. The composite offers multiple features such as good hydrophilic properties, high surface area, admirable potential in repeatability tests and being recyclable for several runs without significant loss in its activity under the optimum reaction conditions. Our results showed the superior applicability of this novel nanocatalyst in terms of conversion reaction, yields and turnover frequencies. The structure of the catalyst was characterized using a variety of techniques.     

Thermodynamics of Carbon Dioxide Adsorption on the Protonic Zeolite H‐ZSM‐5

Adsorption of carbon dioxide on H‐ZSM‐5 zeolite (Si:Al=11.5:1) was studied by means of variable‐temperature FT‐IR spectroscopy, in the temperature range of 310–365 K. The adsorbed CO₂ molecules interact with the zeolite Brønsted‐acid OH groups bringing about a characteristic red‐shift of the O? H stretching band from 3610 cm^?1 to 3480 cm^?1. Simultaneously, the ν₃ mode of adsorbed CO₂ is observed at 2345 cm^?1. From the variation of integrated intensity of the IR absorption bands at both 3610 and 2345 cm^?1, upon changing temperature (and CO₂ equilibrium pressure), the standard adsorption enthalpy of CO₂ on H‐ZSM‐5 is ΔH⁰=?31.2(±1) kJ mol^?1 and the corresponding entropy change is ΔS⁰=?140(±10) J mol^?1 K^?1. These results are discussed in the context of available data for carbon dioxide adsorption on other protonic, and also alkali‐metal exchanged, zeolites.     

New light‐colored poly(ether imide)s based on 2,5‐di‐tert‐butylhydroquinone bis(ether anhydride) and aromatic diamines

A series of poly(ether imide)s (PEIs), III _a–k , with light color and good physical properties were prepared from 1,4‐bis(3,4‐dicarboxypheoxy)‐2,5‐di‐tert‐butylbenzene dianhydride ( I ) with various aromatic diamines ( II _a–k ) via a conventional two‐stage procedure that included a ring‐opening polyaddition to yield poly(amic acid)s (PAA), followed by thermal imidization to the PEI. The intermediate PAA had inherent viscosities in the range of 1.00–1.53 dL g^?1. Most of the PEIs showed excellent solubility in chlorinated solvents such as dichloromethane, chloroform, and m‐cresol, but did not easily dissolve in dimethyl sulfoxide and amide‐type polar solvents. The III series had tensile strengths of 96–116 MPa, an elongation at break of 7–8%, and initial moduli of 2.0–2.5 GPa. The glass‐transition temperatures (T_g) and softening temperatures (T_s's) of the III series were recorded between 232 and 285 °C and 216–279 °C, respectively. The decomposition temperatures for 10% weight loss all occurred above 511 °C in nitrogen and 487 °C in air. The III series showed low dielectric constants (2.71–3.54 at 1 MHz), low moisture absorption (0.18–0.66 wt %), and was light‐colored with a cutoff wavelength below 380 nm and a low yellow index (b^*) values of 7.3–14.8. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1270–1284, 2005     

The diselanylbis(1,3‐dimethyl‐1H‐imidazol‐3‐ium) dication stabilized by the polymeric catena‐pentachloridotricuprate(I) anion

In the title compound, catena‐poly[diselanylbis(1,3‐dimethyl‐1H‐imidazol‐3‐ium) [μ₃‐chlorido‐tetra‐μ₂‐chlorido‐tricuprate(I)]], {(C₁₀H₁₆N₄Se₂)[Cu₃Cl₅]}_n, the diselenide dication is stabilized by catena‐[Cu₃Cl₅]²⁻ anions which associate through strong Cu—Cl bonds [average length = 2.3525 (13) Å] to form polymeric chains. The polymeric [Cu₃Cl₅]²⁻ anion contains crystallographically imposed twofold rotation symmetry, with distorted trigonal‐planar and tetrahedral geometries around the two symmetry‐independent Cu atoms. Likewise, the Se—Se bond of the cation is centered on a twofold rotation axis.     

Transparent,Ultrahigh‐Gas‐Barrier Films with a Brick–Mortar–Sand Structure

Transparent and flexible gas‐barrier materials have shown broad applications in electronics, food, and pharmaceutical preservation. Herein, we report ultrahigh‐gas‐barrier films with a brick–mortar–sand structure fabricated by layer‐by‐layer (LBL) assembly of XAl‐layered double hydroxide (LDH, X=Mg, Ni, Zn, Co) nanoplatelets and polyacrylic acid (PAA) followed by CO₂ infilling, denoted as (XAl‐LDH/PAA)_n‐CO₂. The near‐perfectly parallel orientation of the LDH “brick” creates a long diffusion length to hinder the transmission of gas molecules in the PAA “mortar”. Most significantly, both the experimental studies and theoretical simulations reveal that the chemically adsorbed CO₂ acts like “sand” to fill the free volume at the organic–inorganic interface, which further depresses the diffusion of permeating gas. The strategy presented here provides a new insight into the perception of barrier mechanism, and the (XAl‐LDH/PAA)_n‐CO₂ film is among the best gas barrier films ever reported.     

Michael addition polymerizations of difunctional amines (AA′) and triacrylamides (B3)

Novel hyperbranched poly(amido amine)s containing tertiary amines on the backbones and acryl or secondary amines as the surface groups were successfully synthesized via the Michael addition polymerizations of a triacrylamide [1,3,5‐triacryloylhexahydro‐1,3,5‐triazine (TT)] and a difunctional amine [n‐butylamine (BA)] NMR techniques were used to clarify the structures of hyperbranched polymers and polymerization mechanism. The reactivity of the secondary amine formed in situ was much lower than that of the primary amines in BA. When the feed molar ratio was 1:1 TT/BA, the secondary amine formed in situ was almost kept out of the reaction before the BA (AA′) and TT (B₃) monomers were consumed, and this led to the formation of A′B₂ intermediates containing one secondary amine group and two acryl groups. The self‐polymerization of the A′B₂ intermediates produced hyperbranched polymers bearing acryl as surface groups. For the polymerization with the feed molar ratio of 1:2 TT/BA, A′₂B intermediates containing one acryl group and two secondary amine groups were accumulated until self‐polymerization started; the self‐polymerization of the intermediates formed hyperbranched polymers with secondary amines as their surface groups. Modifications of surface functional groups were studied to form new hyperbranched polymers. The hyperbranched poly(amido amine)s were amorphous. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6226–6242, 2006     

Transparent,Ultrahigh‐Gas‐Barrier Films with a Brick–Mortar–Sand Structure

Transparent and flexible gas‐barrier materials have shown broad applications in electronics, food, and pharmaceutical preservation. Herein, we report ultrahigh‐gas‐barrier films with a brick–mortar–sand structure fabricated by layer‐by‐layer (LBL) assembly of XAl‐layered double hydroxide (LDH, X=Mg, Ni, Zn, Co) nanoplatelets and polyacrylic acid (PAA) followed by CO₂ infilling, denoted as (XAl‐LDH/PAA)_n‐CO₂. The near‐perfectly parallel orientation of the LDH “brick” creates a long diffusion length to hinder the transmission of gas molecules in the PAA “mortar”. Most significantly, both the experimental studies and theoretical simulations reveal that the chemically adsorbed CO₂ acts like “sand” to fill the free volume at the organic–inorganic interface, which further depresses the diffusion of permeating gas. The strategy presented here provides a new insight into the perception of barrier mechanism, and the (XAl‐LDH/PAA)_n‐CO₂ film is among the best gas barrier films ever reported.     

Synthesis and self‐assembly of amphiphilic macrocyclic block copolymer topologies

We demonstrated the synthesis of miktoarm star block copolymers of AB, AB₂, and A₂B, in which block A consisted of linear poly(tert‐butyl acrylate) (P^tBA) and block B consisted of cyclic polystyrene. These structures were produced using the atom transfer radical polymerization to make telechelic polymers that, after modification, were further coupled together by copper‐catalyzed “click” reactions with high coupling efficiency. Deprotection of P^tBA to poly(acrylic acid) (PAA) afforded amphiphilic miktoarm structures that when micellized in water gave vesicle morphologies when the block length of PAA was 21 units. Increasing the PAA block length to 46 units produced spherical core‐shell micelles. AB₂ miktoarm stars packed more densely into the core compared to its linear counterpart (i.e., a four times greater aggregation number with approximately the same hydrodynamic diameter), resulting in the PAA arms being more compressed in the corona and extending into the water phase beyond its normal Gaussian chain conformation. These results show that the cyclic structure attached to an amphiphilic block has a significant influence on increasing the aggregation number through a greater packing density. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.