Haemocompatibility of Ti-3Zr-2Sn-3Mo-25Nb biomedical alloy with surface heparinization using electrostatic self assembly technology

The haemocompatibility of Ti-3Zr-2Sn-3Mo-25Nb biomedical alloy was studied after surface heparinization. A layer of sol-gel TiO2 films was applied on the alloy samples followed by active treatment in the bio-functionalized solution for introducing the OH- and groups, and then the heparin was immobilized on the active TiO2 films through the electrostatic self assembly technology. It is shown that the heparinized films are mainly composed of anatase and rutile with smooth and dense surface. In vitro blood compatibility was evaluated by haemolysis test, clotting time and platelet adhesion behavior tests. The results show that the haemocompatibility of the alloy could be significantly improved by surface heparinization.

Gradient nanoporous phenolics as substrates for high-flux nanofiltration membranes by layer-by-layer assembly of polyelectrolytes

Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly permeable gradient phenolic membranes with tight selectivity are used as substrates to prepare TFC membranes with high permeances by the layer-by-layer assembly method. The negatively charged phenolic substrates are alternately assembled with polycation polyethylenimine(PEI) and polyanion poly(acrylic acid)(PAA)as a result of electrostatic interactions, forming thin and compact PEI/PAA layers tightly attached to the substrate surface. Benefiting from the high permeances and tight surface pores of the gradient nanoporous structures of the substrates, the produced PEI/PAA membranes exhibit a permeance up to 506 L? m-2?h-1?MPa-1, which is ~2–10 times higher than that of other membranes with similar rejections. The PEI/PAA membranes are capable of retaining N 96.1% of negatively charged dyes following the mechanism of electrostatic repulsion. We demonstrate that the membranes can also separate positively and neutrally charged dyes from water via other mechanisms.This work opens a new avenue for the design and preparation of high-flux NF membranes, which is also applicable to enhance the permeance of other TFC membranes.

Preparation of Bentonite Supported Nano Titanium Dioxide Photocatalysts by Electrostatic Self-assembly Method

Electrostatic self-assembly method （ESAM） was used to prepare bentonite supported-nano titanium dioxide photocatalysts. The materials were characterized by X-ray diffraction （XRD）, fourier transform infrared spectroscopy （FT-IR） and scanning electron microscopy （SEM）. Methyl orange was used to estimate the photocatalytic activity of the materials. The effects of the calcination temperature and silane dosage on the photocatalytic activity of the samples were investigated. The experimental results show that the bentonite facilitates the formation of anatase and restrains the transformation of anatase to rutile. Part of nano-size TiO2 particles insert into the galleries of bentonite. The photocatalysts exhibit a synergistic effect of adsorption and photocatalysis on methyl orange. Photocatalysts prepared by ESAM method exhibit higher photocatalytic activity and better recycle ability than those of the traditional method.

Novel layer-by-layer assembly of rGO-hybridised ZnO sandwich thin films for the improvement of photo-catalysed hydrogen production

Metal oxide semiconductor materials such as ZnO have tremendous potential as light absorbers for photocatalysed electrodes in the electrochemical reduction of water. Promoters such as rGO have been added to reduce the recombination losses of charge carriers and improve its photoelectrochemical activity. In this study, the effect of layer ordering on the charge transfer properties of rGO-hybridised ZnO sandwich thin films for the photo-catalysed electrochemical reduction of water was investigated. rGO-hybridised ZnO sandwich thin films were prepared via a facile electrode position technique using a layer-by-layer approach. The thin films were analysed using FESEM, XRD, Raman, PL, UV–vis, EIS and CV techniques to investigate its morphological, optical and electrochemical properties. The FESEM images show the formation of distinct layers of rGO and ZnO nanorods/flakes via the layer-by-layer method. XRD confirmed the wurtzite structure of ZnO. PL spectroscopy revealed a reduction of photoemission intensity in the visible region（580 nm） when rGO was incorporated into the ZnO thin film. Among the six thin films prepared, ZnO/rGO showed superior performance compared to the other thin films（0.964 m A/cm） due to the presence of graphene edges which participate as heterogenous electrocatalysts in the photocatalysed electrolysis of water. rGO also acts as electron acceptor, forming an n-p heterojunction which improves the activity of ZnO to oxidise water molecules to O2. EIS revealed that the application of rGO as back contact（rGO/ZnO, rGO/ZnO/rGO） reduces the charge transfer resistance of a semiconductor thin film. Alternatively, rGO as front contact（ZnO/rGO, rGO/ZnO/rGO） improves the photo-catalysed electrolysis of water through the participation of the rGO edges in the chemical activation of water. The findings from this study indicate that the layer ordering significantly affects the thin film＇s electrostatic properties and this understanding can be further advantageous for tunable applications.

Fabrication of TiO_2 Thin Film by Electrostatic Self-Assembly Method on Optical Fiber

Anionic surfactant sodium lauryl sulfate(SDS), cationic surfactant palmityl trimethyl ammonium chloride(CTAC) and TiO_2 were used to prepare multilayer films on quartz optic fibers by the electrostatic self-assembly (ESA) method. The whole self-assemble process, the function of surfactant and the effect of TiO_2 slurry′s concentration to the self-assemble were discussed. The isoelectric point of TiO_2 slurry measured by experiment is 6.8. The results show that whatever the concentration of the TiO_2 dispersion, a flat and compact adsorbed monolayer on the optic fiber can be built in a stable dispersion at lower pH. There is a adsorbed equilibrium on the substrate (fiber)/solution interface when enough time of incubation is given. A rough and loosen adsorbed layer is formed on the fiber surface by immersed the substrate in a high pH dispersion (pH>10) because the presence of hydroxyl on particle surface. Film thickness can be controlled by controlling the number of layers in the film.

Gold Nanoparticulate Thin Films Fabricated by the Electrostatic Self-Assembly Process

Gold colloids were prepared by citrate-induced reduction of hydrogen tetrachloroaurale, and gold nanoparticles were electrostatically self-assembled with poly( diallyldimethylammonium chloride) into multi-layer thin films on si/icon and quartz substrates. The paniculate thin films were characterized by UV-vis spea-troscopy, surface, enhanced Raman scattering, atomic force microscopy and resistivity measurements. Due to the interparticle coupling between individual gold particles, an obvious collective particle plasmon resonance was ob-served on UV-vis spectra , and the particulate thin films exhibited a strong SERS effect. For multilayer thin films with a high particle coverage on substrates , resistivity of the order of 10-4 Ω·cm was yielded.

In vitro corrosion and antibacterial properties of layer-by-layer assembled GS/PSS coating on AZ31 magnesium alloys

To enhance the corrosion resistance of magnesium（Mg） alloy and to impart its surface with antibacterial functionality for inhibiting biofilm formation and biocorrosion, Mg（OH）2 films were fabricated on AZ31 magnesium alloy substrates by an in-situ hydrothermal method and well-defined multilayer coatings, consisting of gentamicin sulfate（GS） and poly（sodium 4-styrene sulfonate）（PSS）, were prepared via layer-by-layer（Lb L） assembly. The morphologies, chemical compositions and corrosion resistance of the obtained（PSS/GS）n/Mg sample were investigated using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, electrochemical methods and immersion tests. Finally, the bactericidal activity of（PSS/GS）n/Mg samples against Staphylococcus aureus was assessed by the zone of inhibition methods and plate-counting method. The so-synthesized composite coating on the Mg alloy substrates exhibits good corrosion resistance and antibacterial performance, which make them attractive as coatings for medical implanted devices.

In vitro corrosion resistance and antibacterial properties of layer-by-layer assembled chitosan/poly-L-glutamic acid coating on AZ31 magnesium alloys

Surface functionalization of magnesium(Mg)alloys is desired to obtain the surfaces with both improved corrosion resistance and antibacterial property.A corrosion-resistant and antimicrobial coating was prepared on Mg alloy surface by layer-by-layer(LbL)assembly of chitosan(CHI)and poly-L-glutamic acid(PGA)by electrostatic attraction.The functionalized surfaces of the Mg alloys were characterized by field-emission scanning electron microscopy(FE-SEM),Fourier transform infrared(FT-IR)spectroscopy and electrochemical tests.The bactericidal activity of the samples against Staphylococcus aureus was assessed by the zone of plate-counting method.The obtained coating on the Mg alloy substrates exhibits good corrosion resistance and antibacterial performance.

In vitro corrosion resistance,antibacterial activity and cytocompatibility of a layer-by-layer assembled DNA coating on magnesium alloy

A chitosan/deoxyribonucleic acid(CHI/DNA)_(5)coating was constructed by layer-by-layer(LbL)assembly dip coating method with Mg(OH)_(2)coating as an inner protective layer on AZ31 alloy.X-ray diffractometry,X-ray photoelectron spectrometry,Fourier transform infrared spectroscopy and field-emission scanning electron microscopy were utilized to represent the chemical compositions and surface morphologies of the coatings.Electrochemical tests and hydrogen evolution measurements were implemented to confirm the good corrosion resistance of the composite coating in artificial body fluid.Antimicrobial activity of the composite coatings was tested via the plate-counting method,and the cytotoxicity of the samples was appraised by MTT assay and Live/dead staining.A double action was put into effect for the composite coating,which the inner Mg(OH)2 coating plays the part of physical barrier,and the outer(CHI/DNA)5 coating is employed as an inducer to fabricate a biocompatible Ca-P corrosion product coating during immersion,making up for its thin thickness.Otherwise,the composite coating is also beneficial for the growth of bone,resulting from the biomineralization effect of the outer polyelectrolyte multilayer.The good antibacterial property of the(CHI/DNA)5/Mg(OH)2 coating is ascribed to the contact-killing strength of CHI.Thus,the obtained(CHI/DNA)5/Mg(OH)2 coating has a wide application prospect in the field of Mg-based bone implantation.

Power-Dependent Luminescence of CdSe/ZnS Nanocrystal Assembled Layer-by-Layer on a Silver Nanorod Array

We investigate the power-dependent luminescence of CdSe/ZnS semiconductor quantum dots closely packed layer- by-layer in the proximity of a silver nanorod array cavity. It is found that the emission peak shifts significantly to the longer wavelengths as the excitation power increases, especially when the longitudinal surface plasmon resonance of the Ag nanorod array cavity is adjusted to be close to the emission wavelength. The equivalent gain varies with the coating layer of CdSe/ZnS semiconductor quantum dots and the excitation power is also studied to explain this interesting spectrum-shifting effect. These findings could find applications in the dynamic information processing of active plasmonic and photonic nanodevices.

Assembly and Electrochemical Study of Transition Metal Substituted Polyoxometalates SiW_(11)NiO_(39)^(6-) and SiW_(11)MnO_(39)^(6-) on 4-Aminothio-phenol Modified Glassy Carbon Electrode

Via layer-by-layer assembly, the polyoxometalates of Keggin type, SiW_ 11O_ 39Ni(H_2O) 6-(SiNiW_ 11) and {SiW_ 11O_ 39Mn(H_2O) 6-}(SiMnW_ 11) were first immobilized on a 4-aminothiophenol(4-ATP) modified glassy carbon electrode surface. The electrochemical behavior of these polyoxometalates was investigated. They exhibited some special properties in the films, which are different from those in a homogeneous aqueous solution. Their reaction mechanism in a multilayer film is proposed. The electrocatalytic behavior of these multilayer film electrodes for the reduction of BrO-_3 and NO-_2 were comparatively studied.

Method of Spectrophotometric Microanalysis Based on HRP/PET Self-assembly Film

Horseradish peroxidase monolayer was assembled on the surface of PET-CO2 substrate. The reaction kinetics of HRP/PET film and H2O2 in micro reactor was studied using improved spectrophotometer. The relative activity of self-assembly HRP/PET film still remains above 80% after storing for 150 days at 4℃. When applied to determination of H2O2 in sample, the recoveries of H2O2 are 96.5%~101.1%.

Layer-by-layer nanostructured protein loaded nanoparticles: A feasibility study using lysozyme as model protein and chitosan as coating material

Stabilization of proteins in delivery devices and design of appropriate protein carriers are major research issues due to the extreme sensitivity of proteins.Previously,negatively charged nanoparticles,consisting of poly(lactic-co-glycolic acid)(PLGA)and poly(styrene-co-4–styrene-sulfonate)(PSS),showed considerably high loading capacity for positively charged model protein lysozyme depending on the surface charge density of nanoparticles.

BASE-INDUCED RELEASE OF MOLECULES FROM HYDROGEN BONDING DIRECTED LAYER-BY-LAYER FILM

On the basis of hydrogen bonding directed layer-by-layer (LbL) assembly we have fabricated two multilayersystems, poly(acrylic acid) bearng spironaphthoxazine (PAA-SO)/poly(4-vinylpyridine) and carboxyl-terminated polyetherdendrimer (dendrimer-COOH)/poly(4-vinylpyridine). UV-Vis spectroscopy indicates that either PAA-SO or dendrimer-COOH can be released from the corresponding multilayer assemblies upon immerssion in a basic aqueous solution.Furthermore, the rate of molecule release can be controlled either by changing the pH value or by adjusting the layerstructure.

Induction of Superhydrophobicity in a Cellulose Substrate by LbL Assembly of Covalently Linked Dual-Sized Silica Nanoparticles Layers

Micro/nano texturized oxidized cellulose membranes (MNOCM) were constructed by layer-by-layer (LbL) assembly in which a base cellulose film was modified by covalent linkages to amino-functionalized silica nanoparticles (amino-SiO2 NPs, 260 nm diameter) and epoxy-functionalized silica nanoparticles (epoxy-SiO2 NPs, 30 nm diameter). The amino-SiO2 NPs grafted onto the MNOCM surface through a standard amidation reaction between the amino groups of the SiO2 NPs and the carboxyl groups of the MNOCM surface in the presence of EDC and NHS consequently forming a first layer of large (260 nm) nanoparticles;subsequently, it was reacted with smaller (30 nm) epoxy-SiO2 NPs. Continuous repetitions of these alternating sized silica NPs through a standard LbL approach lead to a highly micro/nano-texturized MNOCM film as shown by SEM, which was ultimately sealed with a layer of hydrophobic PFOTES (1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane). Although the wettability of MNOCM was no longer hydrophilic, it was found that at five layers deep of NPs, it became superhydrophobic as evidenced by a water contact angle of 151° ± 2° and slide angle of 4°. The change in wettability was attributed to increases in final LbL layer surface roughness induced by the sufficient LbL layering of alternating sizes of NPs akin to what is observed in a lotus leaf surface. It was also noted that these superhydrophobic-MNOCM materials displayed good self-cleaning.

Positional assembly of multi-enzyme cascade reaction in polyelectrolyte doped microcapsule through electrospray and layer-by-layer assembly

Polyelectrolyte-doped microcapsules(PDM)was fabricated by coaxial electrospray of a mixture of glycerol and water containing 10 mg/mL cationic polyelectrolyte poly(allylamine hydrochloride)(PAH)fed as the core phase solution,and a N,N-dimethylacetylamide solution of 10 wt%polyurethane fed as the shell phase solution.Multienzyme system involving Candida Antarctica lipase B(CALB),glucose oxidase(GOD),and horseradish peroxidase(HRP)for cascade reaction was assembled in the PDM at three different places,namely,surface,shell,and lumen.Placing of enzyme inside aqueous lumen of the PDM was realized by in situ encapsulation through adding the enzyme in the core-phase solution for coaxial electrospray.By ion-pairing of enzyme with cationic surfactant CTAB,an organic soluble enzyme-CTAB complex was prepared,so that in situ embedding of enzyme in the shell of the PDM was realized by adding it into the shell phase solution.Surface attachment of enzymes was achieved by layer-by-layer(LbL)technology,which is based on the ion-exchange interactions between oppositely charged enzymes and PAH that was doped in PDM.The enzyme-decorated microcapsule was then studied as a microbioreactor,in which 1-Oxododecyla-α-glucopyranoside was converted by CALB to glucose,which was oxidised by GOD to gluconolactone in a second step.The hydrogen peroxide produced was then used by HRP to oxidize ABTS to form coloured radical cation ABTS•+for activity analysis.The successful fabrication of the PDM and precise localization of enzymes in the PDM by different strategies were fully characterized.By varying the immobilization strategy,totally six PDM bioreactors with three enzymes precisely positional assembled in different strategies were constructed and their activities for the cascade reaction were investigated and compared.The PDM micro-bioreactor prepared by novel electrospray technologies provide a smart platform for positional assembly of multi-enzyme cascade reaction in a precise and well-controlled manner.

Reagentless biosensor based on layer-by-layer assembly of functional multiwall carbon nanotubes and enzyme-mediator biocomposite

A simple and controllable layer-by-layer （LBL） assembly method was proposed for the construction of reagentless biosensors based on electrostatic interaction between functional multiwall carbon nanotubes （MWNTs） and enzyme-mediator biocomposites. The carboxylated MWNTs were wrapped with polycations poly（allylamine hydrochloride） （PAH） and the resulting PAH-MWNTs were well dispersed and positively charged. As a water-soluble dye methylene blue （MB） could mix well with horseradish peroxidase （HRP） to form a biocompatible and negativelycharged HRP-MB biocomposite. A （PAH-MWNTs/HRP-MB）, bionanomultilayer was then prepared by electrostatic LBL assembly of PAH-MWNTs and HRP-MB on a polyelectrolyte precursor film-modified Au electrode. Due to the excellent biocompatibility of HRP-MB biocomposite and the uniform LBL assembly, the immobilized HRP could retain its natural bioactivity and MB could efficiently shuttle electrons between HRP and the electrode. The incorporation of MWNTs in the bionanomultilayer enhanced the surface coverage concentration of the electroactive enzyme and increased the catalytic current response of the electrode. The proposed biosensor displayed a fast response （2 s） to hydrogen peroxide with a low detection limit of 2.0× 10^-7 mol/L （S/N=3）. This work provided a versatile platform in the further development of reagentless biosensors.

Surface modification of polypropylene non-woven fibers with TiO_2 nanoparticles via layer-by-layer self assembly method:Preparation and photocatalytic activity

Polypropylene（PP） meltblown fibers were coated with titanium dioxide（Ti O2） nanoparticles using layer-by-layer（Lb L） deposition technique. The fibers were first modified with 3layers of poly（4-styrenesulfonic acid）（PSS） and poly（diallyl-dimethylammonium chloride）（PDADMAC） to improve the anchoring of the Ti O2 nanoparticle clusters. PDADMAC, which is positively charged, was then used as counter polyelectrolyte in tandem with anionic Ti O2 nanoparticles to construct Ti O2/PDADMAC bilayer in the Lb L fashion. The number of deposited Ti O2/PDADMAC layers was varied from 1 to 7 bilayer, and could be used to adjust Ti O2 loading. The Lb L technique showed higher Ti O2 loading efficiency than the impregnation approach. The modified fibers were tested for their photocatalytic activity against a model dye, Methylene Blue（MB）. Results showed that the Ti O2 modified fibers exhibited excellent photocatalytic activity efficiency similar to that of Ti O2 powder dispersed in solution. The deposition of Ti O23 bilayer on the PP substrate was sufficient to produce nanocomposite fibers that could bleach the MB solution in less than 4 hr.Ti O2-Lb L constructions also preserved Ti O2 adhesion on substrate surface after 1 cycle of photocatalytic test. Successive photocatalytic test showed decline in MB reduction rate with loss of Ti O2 particles from the substrate outer surface. However, even in the third cycle, the Ti O2 modified fibers are still moderately effective as it could remove more than 95% of MB after 8 hr of treatment.

Electrostatic assembly functionalization of poly(γ-glutamic acid)for biomedical antibacterial applications

Poly(γ-glutamic acid)(γ-PGA)has been found widespread applications in biomedical field because of its excellent water solubility,biocompatibility,and bioactivity.Herein,a water-insoluble γ-PGA antibacterial compound is facilely fabricated via one-pot electrostatic assembly of γ-PGA with cationic ethyl lauroyl arginate(ELA).The functionalized γ-PGA compound(γ-PGA-ELA)ethanol solution can facilely produce colorless and transparent coatings on various inorganic,metal,and polymeric substrates,especially for the lumen of slender catheters(length up to 2 m,and inner diameter down to 1 mm).The functionalized γ-PGA coating presents remarkable antibacterial efficacy in vitro and in vivo.In addition,the γ-PGA compound is used as antibacterial additives of polyolefin via melting extrusion,and the asprepared antibacterial polyolefin demonstrates advantageous antibacterial efficacy.More importantly,the functionalized γ-PGA coating exhibit good hemocompatibility,low cytotoxicity,and satisfactory histocompatibility.The as-proposed γ-PGA compound has a great potential to serve as a safe and multifunctional antibacterial candidate to combat biomedical devices-related infections.

Two-step colloidal synthesis of micron-scale Bi_(2)O_(2)Se nanosheets and their electrostatic assembly for thin-film photodetectors with fast response

Recently discovered bismuth oxychalcogenide(Bi_(2) O_(2) Se) has aroused great interest due to its ultrahigh carrier mobility,tunable band gap and good environmental stability,making it a promising candidate for high-performance electronics and optoelectronics.Their synthesis by colloidal approaches represents a cost-effective alternative to well-established chemical vapor deposition methods,and the resulting electronic-grade inks are important for large-area printed or wearable electronics.However,it is still challenging to control the colloidal growth of Bi_(2) O_(2) Se nanosheets in solution in addition to their assembly into high-performance thin films.Here,we report a two-step colloidal synthesis of Bi_(2) O_(2) Se nanosheets by separating the seeding and growth steps,thereby achieving controllable production of nanosheets with a lateral size of 1.4 mm and a thickness of 10 nm at optimized reaction conditions.These Bi_(2) O_(2) Se nanosheets are electrostatically assembled into large-area thin films,from which a photodetector is fabricated with a responsivity of 6.1 A/W and a short response time of 368 ms under the 520-nm laser illumination.The device exhibits fast response to modulations as high as 100 k Hz,along with a à3 dB bandwidth of 1 kHz.This work provides an important understanding of the controlled colloidal synthesis of Bi_(2) O_(2) Se nanosheets,and demonstrates their potential applications in fast photodetectors.