Comparative bioelectrochemical study of core-shell nanocluster films with ordinary layer-by-layer films containing heme proteins and CaCO3 nanoparticles

Negatively charged heme protein hemoglobin (Hb) or myoglobin (Mb) at pH 9.0 and positively charged poly(diallyldimethylammonium) (PDDA) were alternately adsorbed on the surface of CaCO(3) nanoparticles, forming core-shell CaCO(3)-[PDDA/(protein/PDDA)(m)] ([protein-m]) nanoclusters. Oppositely charged [protein-m] and poly(styrenesulfonate) (PSS) were then assembled layer by layer on various solid substrates, forming {[protein-m]/PSS}(n) films. In the meantime, ordinary layer-by-layer films of heme proteins with CaCO(3) nanoparticles ({protein/CaCO(3)}(n)) were also grown on solid surfaces. Transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) spectroscopy, quartz crystal microbalance (QCM), and cyclic voltammetry (CV) were used to characterize the nanoclusters and monitor the growth of the two types of films. Both kinds of protein films assembled on pyrolytic graphite (PG) electrodes exhibited well-defined, nearly reversible CV reduction-oxidation peaks, characteristic of heme Fe(III)/Fe(II) redox couples, and were used to catalyze the electrochemical reduction of hydrogen peroxide. The {[protein-m]/PSS}(n) films demonstrate distinct advantages over the {protein/CaCO(3)}(n) films due to their larger fraction of electroactive proteins, higher catalytic efficiency, and better thermostability. The penetration experiments of the electroactive probe into these films indicate that the {[protein-m]/PSS}(n) nanocluster films possess more pores or channels than the simple {protein/CaCO(3)}(n) films, which may be beneficial to counterion transport in the charge-hopping mechanism and helpful for the diffusion of catalysis substrates into the films. In addition, the electrochemical and biocatalytic activity of protein nanocluster films can be tailored by controlling the number of bilayers assembled on the nanoparticle cores (m) as well as the film thickness or the number of nanocluster layers on the electrodes (n).     

Electroactive layer-by-layer films of heme protein-coated polystyrene latex beads with poly(styrene sulfonate)

In this work, a novel two-step construction strategy for protein layer-by-layer assembly films was proposed. In the first step, positively charged hemoglobin (Hb) or myoglobin (Mb) at pH 5.0 was adsorbed on the negatively charged surface of 500 nm diameter-sized polystyrene (PS) latex beads, forming core-shell structured PS-protein particles. In the next step, the PS-protein particles were further assembled layer by layer with oppositely charged poly(styrene sulfonate)(PSS) on various solid surfaces under suitable conditions. Cyclic voltammetry (CV), quartz crystal microbalance (QCM), and UV-vis spectroscopy were used to monitor the growth of {(PS-protein)/PSS}(n) films. The stable {(PS-protein)/PSS}(n) films modified on pyrolytic graphite (PG) electrodes demonstrated good electroactivity in protein-free buffer, which was originated from protein heme Fe(III)/Fe(II) redox couples, and the electroactivity extended to six (PS-protein)/PSS bilayers. UV-vis spectroscopy showed that Hb and Mb in the films retained their near-native structure in the medium pH range. {(PS-protein)/PSS}(n) films catalyzed electrochemical reduction of oxygen, hydrogen peroxide, trichloroacetic acid (TCA) and nitrite with a significant lowering of overpotential, and displayed better catalytic activity than corresponding cast PS-protein films.     

Driving forces for layer-by-layer self-assembly of films of SiO2 nanoparticles and heme proteins

Heme protein hemoglobin (Hb) or myoglobin (Mb) and silica nanoparticles in a variety of charge states were assembled layer-by-layer into films on solid surfaces to investigate the driving forces for film assembly. Cyclic voltammetry (CV), quartz crystal microbalance (QCM), X-ray photoelectron spectroscopy (XPS), and UV-vis and reflectance absorption infrared (RAIR) spectroscopy were used to characterize the different [SiO2/protein]n films. Even when the proteins and silica were both negatively charged, stable layer-by-layer [SiO2/protein]n films were successfully fabricated, although amounts of protein were smaller than when nanoparticles and proteins had opposite charges. Results suggest the importance of localized Coulombic attractions between the negative nanoparticle surface and positively charged amino acid residues on the Mb or Hb surfaces in the assembly and for the stability of [SiO2/protein]n films.     

Surface stress, thickness, and mass of the first few layers of polyelectrolyte

The effects of surface stress and mass loading upon the adsorption of polyelectrolytes onto flexible silicon micromechanical cantilever sensors (MCSs) were studied in situ. A self-assembled monolayer of 2-mercaptoethylamine chloride (2-MEA) on gold was used to achieve single-side adsorption on the MCS. Such a preparation gave a positive surface potential, whereas a bare SiOx surface gave a negative surface potential. Wide scan X-ray photoelectron spectroscopy confirmed that the adsorption of polystyrenesulfonate (PSS) and polyallylamine hydrochloride (PAH) followed the general rule expected from the electrostatic interaction between the substrate and the polyelectrolyte, whereas the adsorption polyethyleneimine (PEI) did not. The adsorption of PAH on SiO(x) from a 3 mM water solution containing 1 M NaCl was associated with a deflection of the MCS toward the polyelectrolyte monolayer (tensile surface stress) owing to the hydrogen bonding between neighboring amino groups. Here, a surface stress change of 1.4 +/- 0.1 N/m was estimated. The adsorption of PSS from a 3 mM water solution containing 1 M NaCl on a 2-MEA surface induced a deflection of the MCS away from the polyelectrolyte layer (compressive stress), toward the SiO(x) side. Here, a surface stress change of 3.1 +/- 0.3 N/m was determined. The formation of a PAH layer on top of the PSS layer resulted in a deflection of the MCS toward the PAH layer. This indicated that the adjacent PSS layer was deswelling, corresponding to a surface stress change of 0.5 +/- 0.1 N/m.     

Effect of precursor-layer surface charge on the layer-by-layer assembly of polyelectrolyte/nanoparticle multilayers

In this Article, we investigate the effect of a precursor layer, which is composed of four bilayers of polyethyleneimine (PEI) and poly(sodium styrene sulfonate) (PSS), on the subsequent LBL assembly of hybrid films composed of indium tin oxide (ITO) nanoparticles and PSS. A precursor polyelectrolyte layer is usually deposited to minimize interference by the substrate. It is shown here that the "effective" surface charge of the precursor layer can significantly affect the subsequent assembly behavior of [ITO/PSS](9.5) hybrid thin films. Depending on the surface charge of the precursor layer, the subsequent LbL assembly of [ITO/PSS](9.5) hybrid films can exhibit either one or two regimes. When two growth regimes are present, the first one consists of a "recovery regime", and the second is the expected "linear growth regime." The length of the "recovery regime" is dependent on how much positive charge the precursor layer possesses and how fast this surface charge can be compensated. This work reveals for the first time that changes in the surface charge of the precursor layer can have a significant effect on the subsequent LBL assembly process. The surface charge of the precursor layer was investigated using ζ-potential measurements on model silica microspheres. These experiments showed that the surface charge of the precursor layer, [PEI/PSS](4), is dependent on the pH of the solution in which it is immersed, and that it can reverse from a negatively charged surface to a positively charged one, at sufficiently low pH due to the protonation of PEI, despite having the negatively charged PSS layer as the outermost layer.     

Redox processes of cytochrome c immobilized on solid supported polyelectrolyte multilayers

The heme protein cytochrome c (Cyt-c), immobilized on polyelectrolyte multilayers on a silver electrode, was studied by stationary and time-resolved surface-enhanced resonance Raman (SERR) spectroscopy to probe the redox site structure and the mechanism and dynamics of the potential-dependent interfacial processes. The layers were built up by sequential adsorption of polycations (poly[ethylene imine] (PEI); polyallylamine hydrochloride (PAH)) and polyanions (poly[styrene sulfonate] (PSS)). All multilayers terminated by PSS electrostatically bind Cyt-c. On PEI/PSS coatings, Cyt-c is peripherally bound and fully redox-active. Due to the interfacial potential drop, the apparent redox potential is lowered by 40 mV compared to that in solution. The rate constant for the heterogeneous electron transfer (ET) of ca. 0.1 s(-1) is consistent with electron tunneling through largely ordered PEI/PSS layers. ET is coupled to a reversible conformational transition of Cyt-c that involves a change of the coordination pattern of the heme. Additional (PAH/PSS) double layers cause a broadening of the redox transition and a drastic negative shift of the redox potential, which is attributed to the formation of PSS/Cyt-c complexes. It is concluded that Cyt-c can effectively compete with PAH for binding of PSS, resulting in a rearrangement of the layered structure and a penetration of the PSS-bound Cyt-c into the PAH/PSS double layers. This conclusion is consistent with SERR intensity and quartz microbalance measurements. ET was found to be overpotential-independent and faster than that for PEI/PSS coatings, which is interpreted in terms of specific PSS/Cyt-c complexes serving as gates for the heterogeneous ET.     

Layer-by-layer films of hemoglobin or myoglobin assembled with zeolite particles: electrochemistry and electrocatalysis

Positively charged hemoglobin (Hb) or myoglobin (Mb) at pH 5.0 in solutions and negatively charged zeolite particles in dispersions were alternately adsorbed onto solid surfaces forming [zeolite/protein](n) layer-by-layer films, which was confirmed by quartz crystal microbalance (QCM) and cyclic voltammetry (CV). The protein films assembled on pyrolytic graphite (PG) electrodes exhibited a pair of well-defined, nearly reversible CV peaks at about -0.35 V vs. SCE at pH 7.0, characteristic of the heme Fe(III)/Fe(II) redox couples. Hydrogen peroxide (H(2)O(2)) and nitrite (NO(2)(-)) in solution were catalytically reduced at [zeolite/protein](7) film modified electrodes, and could be quantitatively determined by CV and amperometry. The shape and position of infrared amide I and II bands of Hb or Mb in [zeolite/protein](7) films suggest that the proteins retain their near-native structure in the films. The penetration experiments of Fe(CN)(6)(3-) as the electroactive probe into these films and scanning electron microscopy (SEM) results indicate that the films possess a great amount of pores or channels. The porous structure of ]zeolite/protein](n) films is beneficial to counterion transport, which is crucial for protein electrochemistry in films controlled by the charge-hopping mechanism, and is also helpful for the diffusion of catalysis substrates into the films. The proteins with negatively charged net surface charges at pH 9.0 were also successfully assembled with like-charged zeolite particles into layer-by-layer films, although the adsorption amount was less than that assembled at pH 5.0. The possible reasons for this were discussed, and the driving forces were explored.     

Layer-by-layer enzyme/polyelectrolyte films as a functional protective barrier in oxidizing media

The influence of a catalase (Cat) layer located at different depths in the layer-by-layer hemoglobin/polystyrene sulfonate films with an (Hb/PSS)(20)(-)(x)/(Cat/PSS)/(Hb/PSS)(x) (x = 0-20) architecture on kinetics of hemoglobin degradation under treatment with hydrogen peroxide solutions of different concentrations and features of H(2)O(2) decay in surrounding solutions has been studied. While assembled on the top of the multilayers, the catalase layer shows the highest activity in hydrogen peroxide decomposition. Hemoglobin in such films retains its nativity for a longer period of time. The effect of catalase layers is compared with that of protamine, horseradish peroxidase, and inactivated catalase. Positioning an active layer with catalytic properties as an outer layer is the best protection strategy for layer-by-layer assembled films in aggressive media.     

Fabrication of electroactive layer-by-layer films of myoglobin with gold nanoparticles of different sizes

Alternate adsorption of oppositely charged myoglobin (Mb) and gold nanoparticles with different sizes were used to assemble {Au/Mb}n layer-by-layer films on solid surfaces by electrostatic interaction between them. The direct electrochemistry of Mb was realized in {Au/Mb}n films at pyrolytic graphite (PG) electrodes, showing a pair of well-defined, nearly reversible cyclic voltammetry (CV) peaks for the Mb heme FeIII/FeII redox couple. Quartz crystal microbalance (QCM), electrochemical impedance spectroscopy (EIS), and CV were used to monitor or confirm the growth of the films. Compared with other Mb layer-by-layer films with nonconductive nanoparticles or polyions, {Au/Mb}n films showed much improved properties, such as smaller electron-transfer resistance (Rct) measured by EIS with Fe(CN)3-/4- redox probe, higher maximum surface concentration of electroactive Mb (Gamma*max), and better electrocatalytic activity toward reduction of O2 and H2O2, mainly because of the good conductivity of Au nanoparticles. Because of the high biocompatibility of Au nanoparticles, adsorbed Mb in the films retained its near native structure and biocatalytic activity. The size effect of Au nanoparticles on the electrochemical and electrocatalytic activity of Mb in {Au/Mb}n films was investigated, demonstrating that the {Au/Mb}n films assembled with smaller-sized Au nanoparticles have smaller Rct, higher Gamma*max, and better biocatalytic reactivity than those with larger size.     

Effect of chain length and charge density on the construction of polyelectrolyte multilayers on colloidal particles

Two combinations of sodium poly(4-styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) of different chain length and charge density are employed to construct multilayer films. The polyelectrolytes are assembled layer-by-layer on colloidal particles in the absence of salt. We have investigated the formation and electrical characteristics of the films by using electric light scattering technique. The results show that the film thickness is independent of the chain length when fully charged PAH (at pH 4.6) is combined with fully charged PSS. When the films are prepared with less charged PAH (at pH 6.7) and fully charged PSS, lower thickness is found for the film with shorter polymer chains. In all cases, the thickness increment realized on addition of the polymer with lower molar concentration is partially lost on exposure to the solution with higher concentration of the oppositely charged partner. When the film growth is regular (at equal molar concentrations of the fully charged polyelectrolytes), the ratio of PSS to PAH charge, estimated from the electro-optical effect values, exceeds 1. The electro-optical effect is also higher for the films ending with PSS when fully charged PSS is combined with less charged PAH (at pH 6.7). This reveals the key role of the charge in the last-adsorbed layer for the electro-optical behavior of the whole film.     

Characteristics of polyelectrolyte multilayers: effect of PEI anchoring layer and posttreatment after deposition

The influence of a first (anchoring) layer and film treatment on the structure and properties of polyelectrolyte multilayer (PEM) films obtained from polyallylamine hydrochloride (PAH) and polysodium 4-styrenesulfonate (PSS) was studied. Branched polyethyleneimine (PEI) was used as an anchoring layer. The film thickness was measured by ellipsometry. Complementary X-ray reflectometry and AFM experiments were performed to study the change in the interfacial roughness. We found that the thickness of the PEM films increased linearly with the number of layers and depended on the presence of an anchoring PEI layer. Thicker films were obtained for multilayers having PEI as the first layer comparing to films having the same number of layers but consisting of PAH/PSS only. We investigated the wettability of PEM surfaces using direct image analysis of the shape of sessile water drops. Periodic oscillations in contact angle were observed. PAH-terminated films were more hydrophobic than films with PSS as the outermost layer. The effect of long time conditioning of PEM films in solutions of various pH's or salt (NaCl) concentrations was also examined. Salt or base solutions induced modification in wetting properties of the polyelectrolyte multilayers but had a negligible effect on the film thickness.     

以聚电解质多层膜为纳米反应器制备Au@Pt核壳纳米粒子

以聚二烯丙基二甲基氯化铵和聚苯乙烯磺酸钠为构筑单元,通过静电层层自组装制备了多层膜,利用薄膜中存在的抗衡阴离子,选择AuCl-4和PtCl2-6作为Au和Pt的前驱体,通过连续的阴离子交换/还原,原位制备了Au-Pt双金属纳米粒子。 紫外-可见分光光度法、透射电子显微镜和能量色散X射线能谱数据表明,在聚电解质多层薄膜中成功地制备了具有核壳结构的Au@Pt双金属纳米粒子。 这种纳米粒子在电化学催化、燃料电池方面具有潜在的应用价值。     

Lanthanide antimony oxohalides: from discrete nanoclusters to inorganic-organic hybrid chains and layers

Structures à la carte: The combination of lone pairs and halide ions yields a praseodymium antimony oxohalide nanocluster [Pr(4) Sb(12) O(18) Cl(17) ](5-) with nearly perfect T(d) symmetry. Inorganic-organic hybrid compounds with 1D chain structure and 2D wave layer structure were assembled using dicarboxylic ligands with angular or linear geometry to interconnect the nanoclusters as secondary building units (see picture; purple Pr, red O, blue Sb, green Cl).     

Synthesis, characterization, and activity in ethylene polymerization of silica supported cationic cyclopentadienyl zirconium complexes

Cp*ZrMe3 reacts with silica pretreated at 800 degrees C, SiO(2-(800)) through two pathways: (a) protolysis of a Zr-Me group by surface silanols and (b) transfer of a methyl group to the surface by opening of strained siloxane bridges, in a relative proportion of ca. 9/1, respectively, affording a well-defined surface species [([triple bond]SiO)ZrCp*(Me)2], 3, but with two different local environments 3a, [([triple bond]SiO)ZrCp*(Me)2][[triple bond]Si-O-Si[triple bond]], and the other with 3b, [structure: see text]. The reaction of the species 3 with B(C6F5)3 is controlled by this local environment and gives three surface species [([triple bond]SiO)ZrCp*(Me)](+)[MeB(C6F5)3]- [[triple bond]Si-O-Si[triple bond]], 4a (20%), [([triple bond]SiO)ZrCp*(Me)](+)[(Me)B(C6F5)3]- [[triple bond]Si-Me], 4b (10%), and [([triple bond]SiO)2ZrCp*](+)[(Me)B(C6F5)(3)](-)[[triple bond]Si-O-Si[triple bond]], 5 (70%). On the contrary, the reaction of Cp*Zr(Me)3, Cp2Zr(Me)2 with [[triple bond]SiO-B(C6F5)3](-)[HNEt2Ph]+, 6, leads to a unique species [([triple bond]SiO)B(C6F5)3](-)[Cp*Zr(Me)2.NEt2Ph]+, 7, and [([triple bond]SiO)ZrCp2](+)[(Me)B(C6F5)3]-, 9 respectively. The complexes 4 and 7 are active catalysts in ethylene polymerization at room temperature, 93 and 67 kg PE mol Zr1- atm(-1) bar(-1), respectively, indicating that covalently bounded Zr catalyst 4 is slightly more active than the "floating" cationic catalyst 7.     

Nanocluster formation and stabilization fundamental studies: ranking commonly employed anionic stabilizers via the development,then application,of five comparative criteria

To start, a brief introduction is provided on the importance of transition-metal nanoclusters, on the need to develop and then apply methods to rank the nanocluster formation and then stabilizing abilities of commonly employed anions, solvents, cations, and polymers, and on the somewhat confused literature of nanocluster stabilization. The fundamental importance of surface-adsorbed anions in transition-metal nanocluster stabilization is noted, the reason the present studies begin with a study of nanocluster-stabilizing anions. Next, five criteria, as well as the associated experimental methods, are developed to evaluate the efficacy of nanocluster stabilizing agents. The criteria are of fundamental significance in that they allow the separation of stabilizing agent effects on nanocluster formation from those on nanocluster stabilization. The results from applying the five criteria to four commonly employed anions lead to the first "anion series" of relative nanocluster-formation and stabilizing abilities, at least for the Ir(0) nanoclusters examined and by the following five criteria: [(P(2)W(15)Nb(3)O(61))(2)O](16-) (a Brphinsted-basic polyoxoanion) > C(6)H(5)O(7)(3-) (citrate trianion) > [-CH(2)-CH(CO(2))-](n)(n-) (polyacrylate) approximately Cl(-). In addition to the needed methods and the first anion series, six other (8 total) conclusions are reached, important insights in an area previously lacking hard information about which anions are the better choices for nanocluster formation and stabilization. The results are also of significance in establishing polyoxoanions, notably highly charged and basic polyoxoanions such as [(P(2)W(15)Nb(3)O(61))(2)O](16)(-), as the present "Gold Standards" among currently known nanocluster stabilizing anions, and according to the above five criteria. Such standards provide a reference point for future work aspiring to develop even better nanocluster stabilizing anions, solvents, cations, and polymers or their combinations.     

Anisole hydrogenation with well-characterized polyoxoanion- and tetrabutylammonium-stabilized Rh(0) nanoclusters: effects of added water and acid, plus enhanced catalytic rate, lifetime, and partial hydrogenation selectivity

Following a comprehensive look at the arene hydrogenation literature by soluble nanocluster catalysts, six key, unfulfilled goals in nanocluster arene hydrogenation catalysis are identified. To begin to address those six goals, well-characterized polyoxoanion- and tetrabutylammonium-stabilized Rh(0) nanoclusters have been synthesized by the reduction of the precisely defined precatalyst [Bu(4)N](5)Na(3)[(1,5-COD)Rh small middle dotP(2)W(15)Nb(3)O(62)] with H(2) in propylene carbonate solvent. These Rh(0) nanoclusters are characterized by their stoichiometry of formation, transmission electron microscopy, and the two rate constants which characterize their mechanism of formation; previous studies in our laboratories have provided additional characterization of polyoxoanion-stabilized Rh(0) nanoclusters. Propylene carbonate solutions of the Rh(0) nanoclusters catalyze the hydrogenation of anisole (methoxybenzene) under mild conditions (22-78 degrees C, 30-40 psig H(2)). Proton donors such as water or HBF(4) small middle dotEt(2)O are discovered to affect both nanocluster formation and nanocluster arene hydrogenation catalysis. Under identical conditions, the Rh(0) nanoclusters are 10-fold more active than a commercially available, oxide-supported 5% Rh/Al(2)O(3) catalyst of the same average metal-particle size. A series of lifetime experiments shows that the Rh(0) nanoclusters are capable of at least 2600 total turnovers (TTO), a lifetime significantly longer than the approximately 100 TTO often seen for nanocluster arene hydrogenation catalysts, and a lifetime slightly better than the prior record of 2000 TTO for a literature nanocluster system. The present polyoxoanion-stabilized Rh(0) nanoclusters also display a record, albeit modest, 30% selectivity for the partial hydrogenation of anisole to 1-methoxycyclohexene with an overall yield of up to 8% at higher temperatures. In comparison to the 5% Rh/Al(2)O(3) catalyst, the polyoxoanion-stabilized nanoclusters yield a 4.7-fold higher maximum yield of 1-methoxycyclohexene. Finally, the seven main findings of the present work are summarized, including how they address five of the aforementioned six main goals in nanocluster arene hydrogenation.     

预混合自组装辣根过氧化物酶生物活性膜及其催化活性研究

以阳离子化的辣根过氧化物酶 (HRP)和阴离子聚苯乙烯磺酸钠 (PSS)的预混合溶液 ,与阳离子聚电解质聚二甲基二烯丙基氯化铵 (PDDA)通过逐层组装 ,在阴离子化聚对苯二酸乙二酯 (PET)表面构建了多层生物活性膜 .用紫外 可见光谱仪 (UV Vis)和原子力显微镜 (AFM)研究了交替自组装膜的结构和表面形膜 ,并测定了自组装膜的生物催化活性 .结果表明 ,预混合溶液中的PSS与HRP一起沉积在PDDA膜层上组装成 (PSS+HRP)膜层 ,且每层中PSS和HRP的比例一致 ;(PSS +HRP)膜层呈条状分布 ,膜表面较为平整 ;多层膜中的HRP催化H2 O2 与 4 氨基安替比林的显色反应的表观米氏常数为 9 7× 10 - 5mol·L- 1 (相对于H2 O2 底物 ) ,较溶液中 (1 5 2× 10 - 4mol·L- 1 )的小 .     

Hybrid Electrochromic Multilayer Films Based on Fe(II)-Metalloviologens and TiO2 Nanoparticles

Metallosupramolecular coordination polyelectrolyte, Fe(II)-metalloviologen(FEN), was prepared by the reaction of Fe(II) with a novel bisterpyridine ligand. As active components, FENs could be assembled into electrochromic multilayer films with negative charged polystyrene sulfate(PSS) by the sequential deposition layer-by-layer technique. Numerous analytical instruments, such as UV-Vis spectroscopy, atomic force microscopy(AFM), tunneling electron microscopy(TEM), zeta-potential measurement and electrochemical measurement have been utilized to characterize their morphology, optical and electrochromic properties. It has been observed that as-prepared films exhibited multi-colour changes by triggering with different potentials. However, the low optical contrast of multilayer films would limit their further applications. In order to overcome this problem, semiconductor TiO₂ nanoparticles(TiO₂) were incorporated into FEN multilayers by layer-by-layer approach. By carefully optimizing the film structure, as-resulted hybrid films containing FEN, TiO₂ and PSS exhibited high optical contrast, suitable response time and long-term stability. Such hybrid films should be promising candidates to meet the requirements for deve- loping flexible displays and electrochromic devices.     

Layer-by-layer assembly of salt-containing polyelectrolyte complexes for the fabrication of dewetting-induced porous coatings

The layer-by-layer (LbL) assembly of salt-containing nonstoichiometric polyelectrolyte complexes (PECs) with oppositely charged uncomplexed polyelectrolyte for the fabrication of dewetting-induced porous polymeric films has been systematically investigated. Salt-containing poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) complexes (noted as PAH-PAA) with a molar excess of PAH were LbL assembled with polyanion poly(sodium 4-styrenesulfonate) (PSS) to produce PSS/PAH-PAA films. The structure of the PAH-PAA complexes is dependent on the concentration of NaCl added to their aqueous dispersions, which can be used to tailor the structure of the LbL-assembled PSS/PAH-PAA films. Porous PSS/PAH-PAA films are fabricated when salt-containing PAH-PAA complexes with a large amount of added NaCl are used for LbL assembly with PSS. In-situ and ex-situ atomic force microscopy measurements disclose that the dewetting process composed of pore nucleation and pore growth steps leads to the formation of pores in the LbL-assembled PSS/PAH-PAA films. The present study provides a facile way to fabricate porous polymeric films by dewetting LbL-assembled polymeric films comprising salt-containing PECs.     

Assembly of layer-by-layer films of electroactive hemoglobin and surfactant didodecyldimethylammonium bromide

When a solid substrate with negative surface charges was placed in an aqueous didodecyldimethylammonium bromide (DDAB) vesicle dispersion, the cationic surfactant DDAB with two hydrocarbon chains could be assembled into the biomembrane-like tail-to-tail double-layer structure on the solid surface with the positively charged head groups toward outside, making the surface charge reverse from negative to positive. After the solid substrate with DDAB was immersed in a hemoglobin (Hb) solution at pH 9.0, the negatively charged Hb was adsorbed on the surface of DDAB layer by electrostatic attraction, forming a DDAB/Hb film. By repeating this adsorption cycle, the {DDAB/Hb}(n) layer-by-layer films were assembled on solid surfaces, which was confirmed by UV-vis spectroscopy, quartz crystal microbalance (QCM), and cyclic voltammetry (CV). The stable {DDAB/Hb}(n) films assembled on pyrolytic graphite (PG) electrodes showed two pairs of nearly reversible redox peaks at about -0.22 and -1.14 V vs SCE in pH 7.0 buffers, characteristic of the Hb heme Fe(III)/Fe(II) and Fe(II)/Fe(I) redox couples, respectively. The direct electrochemistry of Hb in the films could be used to electrocatalyze reduction of various substrates. UV-vis and IR spectroscopic results and comparison experiments with {DDAB/hemin}(n) films indicate that Hb in the {DDAB/Hb}(n) films essentially retains its native structure. Atomic force microscopy (AFM) was used to characterize the morphology of the films with different outermost layers.