Adsorption/desorption behavior of protein on nanosized hydroxyapatite coatings: A quartz crystal microbalance study

Protein separation relates closely to the interactions between proteins and various kinds of adsorbents. To obtain a direct and comprehensive understanding of the protein interaction at the solid/solution interface, quartz crystal microbalance (QCM) technique was employed to in situ investigate the adsorption process of bovine serum albumin (BSA) on nanosized hydroxyapatite coatings, and factors affecting its adsorption such as pH, solution ionic strength and temperature were discussed in detail. The adsorption kinetic parameter and the desorption of adsorbed BSA caused by phosphate buffer solution (PBS) introduction were investigated and discussed as well, and an adsorption/desorption mechanism has been proposed. The obtained information suggests that QCM is a useful method for monitoring the adsorption/desorption behavior of BSA on nanosized hydroxyapatite coating.     

Effects of surface microstructure of hydroxyapatite on protein adsorption and biological performance of osteoblasts

The aim of this study was to investigate the effect of surface microstructure on the serum protein adsorption and the biological performance of osteoblasts cultured in vitro, when seeded onto the surface of ceramics with different grain size: conventional HA, micron-sized HA and nano-sized HA. Sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) was used to comparatively analyze the protein adsorption solution. The content of alkaline phosphatase (ALP) was determined, and then by using wash way method, the adhesion ability was tested. XPS tests indicated that the content of N on the surface was significant different between the three groups (P < 0.05). SDS-PAGE analysis indicated that all the materials in these three groups could adsorb a large amount albumin, while the material in the nHA group adsorbed more albumin than the other groups. There were significant differences among them on the levels of osteoblast proliferation and adhesion in vitro. The biocompatibility of nHA is the best and of conventional HA is the worst.     

Hybrid surface from self-assembled layer and its effect on protein adsorption

We synthesized hybrid self-assembled monolayer (SAM) with short chain hydrophobic and hydrophilic groups on the same molecule. The physical characteristics such as surface roughness and surface energy of the synthesized hybrid SAM were compared with mono SAMs of amine, octyl and mixed amine-octyl SAM. We also compared the response of the surfaces towards adsorption of bovine serum albumin (BSA) using quartz crystal microbalance (QCM). We determined adsorbed amount (Γ) of BSA on the various surfaces from its various bulk concentrations. It follows the Langmuir adsorption isotherm in the concentration range of our study. The strength of adsorbed protein was characterized from the dissipation factor (ΔD). The highest ΔD value of adsorbed BSA was observed for the adsorption on hybrid surface. The arrangement of BSA on hybrid surface such that it leaded to soft layer, corresponded to the highest ΔD value. These findings suggest that the hybrid surface is a potential surface modifying agent of biomaterials.     

双硫腙包覆钛酸锶钡粉体对水中镉的吸附性能

用草酸盐化学共沉淀法合成钛酸锶钡粉体,用双硫腙对该粉体表面进行包覆修饰,制成新型有机包覆吸附剂。用傅里叶变换红外光谱对包覆粉体进行了表征;以火焰原子吸收为检测手段,研究了该吸附剂对水中Cd2+ 的吸附性能,考察了洗脱条件;通过红外光谱,初步探讨了包覆和吸附作用机理。结果表明,双硫腙以氢键作用牢固地包覆于钛酸锶钡粉体上;该包覆粉体对水中的Cd2+具有较高的选择性吸附能力,其吸附量受介质的pH值影响,当pH值小于3时,该吸附剂对水中的Cd2+几乎不吸附,当pH值大于6时,吸附量达到最大;常温下,20 min内吸附达到平衡;吸附在双硫腙包覆钛酸锶钡粉体上的Cd2+,可用5% EDTA溶液完全洗脱。建立了吸附富集,火焰原子吸收法测定水中Cd2+的新方法,方法检出限为0.2 μg·L-1,相对标准偏差为2.9%。应用于自来水和地表水中Cd2+的测定,结果满意。     

XPS and bioactivity study of the bisphosphonate pamidronate adsorbed onto plasma sprayed hydroxyapatite coatings

This paper reports the use of X-ray photoelectron spectroscopy (XPS) to investigate bisphosphonate (BP) adsorption onto plasma sprayed hydroxyapatite (HA) coatings commonly used for orthopaedic implants. BPs exhibit high binding affinity for the calcium present in HA and hence can be adsorbed onto HA-coated implants to exploit their beneficial properties for improved bone growth at the implant interface. A rigorous XPS analysis of pamidronate, a commonly used nitrogenous BP, adsorbed onto plasma sprayed HA-coated cobalt-chromium substrates has been carried out, aimed at: (a) confirming the adsorption of this BP onto HA; (b) studying the BP diffusion profile in the HA coating by employing the technique of XPS depth profiling; (c) confirming the bioactivity of the adsorbed BP. XPS spectra of plasma sprayed HA-coated discs exposed to a 10 mM aqueous BP solution (pamidronate) for periods of 1, 2 and 24 h showed nitrogen and phosphorous photoelectron signals corresponding to the BP, confirming its adsorption onto the HA substrate. XPS depth profiling of the 2 h BP-exposed HA discs showed penetration of the BP into the HA matrix to depths of at least 260 nm. The bioactivity of the adsorbed BP was confirmed by the observed inhibition of osteoclast (bone resorbing) cell activity. In comparison to the HA sample, the HA sample with adsorbed BP exhibited a 25-fold decrease in primary osteoclast cells.     

Study of adsorption of bovine serum albumin to Langmuir-Blodgett film coated surfaces using work of adhesion as a tool

This work reports on the use of rate of change of work of adhesion (ΔW) as a tool to study adsorption of bovine serum albumin (BSA) to glass and Langmuir-Blodgett film of dihexadecyl phosphate (DHP) and dioctadecyl dimethyl ammonium bromide (DOMA) coated surfaces. Pure BSA and BSA with additives - sorbitol and urea - have been adsorbed to bare glass surfaces and DHP and DOMA coated surfaces. The results suggest that an increase in ΔW with time indicates promotion of adsorption while a decrease indicates hindered adsorption. Further adsorption of BSA was most effective on DHP coated surface compared with bare glass and DOMA coated glass. In case of mixtures of BSA with urea and sorbitol, BSA + urea showed hindered adsorption while adsorption of BSA + sorbitol was efficient for all substrates.     

Optimization of surface coating condition using vapor form of alkanethiol on Cu nano powders for the application of oxidation prevention

There has been a growing interest in metal nano powders recently, and researches on Copper (Cu) nano particles are actively pursued due to its good electrical conductivity and its low prices. However, its easiness to oxidation and corrosion has delayed its research progress in Cu nano particles to be applied in inkjet printed electronics and other related research area. To overcome these problems, new surface coating method on Cu nano particles has been developed using dry process instead of conventional wet coating method. Octanethiol was used as a dry coating material because it has sulfur at the end of monolayer to chemically bond to the surface of fresh non-oxidized Cu nano particles to prevent oxidation. Octanethiol does not bond to oxidized surface of Cu nano particles. Previously, bonding between octanethiol and Cu nano particles, more specifically bonding between Cu surface and Sulfur (S) was analyzed using X-ray Photoelectron Spectroscopy (XPS). As a result, S peak was detected on the coated Cu nano particles, indicating that octanethiol chain has been successfully coated on the surface of Cu nano particles.In this study, optimization of dry coating condition was studied by varying coating time and cycles. XPS was used to analyze the composition of coated material to monitor the change in amount of S and O peaks for each condition. It was found that as the amount of Sulfur increased, the amount of Oxygen decreased and vice versa. This finding indicates that dry coating has suppressed the formation of oxygen on the surface of Cu nano powders by surrounding Cu surface with Sulfur end of octanethiol chain. Based on these experiments, the optimum coating condition for suppressing Cu oxidation was found to be 5 min and 6 cycles. For future work, the lifetime of octanethiol layer on the surface of Cu surface needs to be studied.     

基于FTIR,ICP-MS的仿生Mg-Ag-HA/明胶抗菌生物涂层的制备与表征

目前,傅里叶变换红外光谱（FTIR）技术具有待测样品数量少、对特征基团灵敏度高、样品制备和分析简单等优点;电感耦合等离子体质谱（ICP-MS）的优势也较为显著：微量元素的高灵敏度检出率,低检测限和多元素的同时分析;协同上述两种方法,可快速对功能医用材料的化学元素和基团进行鉴定,从而为仿生医用抗菌材料的研发提供新的设计思路和理论依据。羟基磷灰石(HA)因其优异的骨传导和骨诱导特性被用于薄膜材料,钛植入表面HA薄膜已进入临床应用阶段。但是,HA的本真脆性和缺乏抗菌性,常常导致植入失败。因此,开发一种耐磨性好且抑菌性优的促成骨功能涂层成为当前急需要解决的难题。研究目的在于在钛表面制备耐磨性好且抑菌性优的促成骨功能涂层,初步探讨了涂层的抗菌离子缓释规律和生物活性。开拓性地在工业纯钛表面制备了明胶、银和镁离子改性的羟基磷灰石(Mg-Ag-HA/明胶)抗菌涂层。将银(Ag)引入羟基磷灰石涂层(HA)以改善其抗菌性能,镁(Mg)作为第二元素以提高生物相容性,明胶可以同时提高HA的生物相容性和力学性能。ICP-MS测定涂层中镁和银元素的释放量和可持续性。所得到的新型Mg-Ag-HA/明胶的SEM结果、Ca/P比值、化学特征峰和晶相通过FTIR, SEM,EDAX和XRD进行表征。结果表明：明胶的羧基与HA的钙离子之间已形成Ca-COO化学键,明胶和Mg-Ag-HA构成了有机-无机复合涂层;Mg和Ag元素被成功地引入到了HA晶格中,且分布均匀。模拟体液浸泡后,Mg-Ag-HA/明胶涂层试样表面有新的缺钙型的HA生成,且球形磷灰石中检测到新的Mg,Na和Cl元素;结果表明,新型复合涂层样品具有良好的生物活性。SEM和LSCM实验结果观察发现,小鼠颅骨成骨细胞在Mg-Ag-HA/明胶上粘附良好,细胞伸展大量伪足,未见细胞毒性。明胶的加入大大降低了复合镀层中Mg2+和Ag+的释放速率,提高了复合镀层的生理稳定性,为镀层保持长期抗菌功能提供了保证。Mg-Ag-HA/明胶作为钛基涂层材料具有良好的抗菌离子释放能力和优异的生物相容性,为新型抗感染外科植入体的研发提供了新思路。     

Apatite formation on Poly (vinyl alcohol)-coated Poly (?-caprolactone) films by incubation in simulated body fluids

In this study, biodegradable poly (?-caprolactone) (PCL) films were coated with poly (vinyl alcohol) (PVA) and then incubated in a simulated body fluid 1.5SBF to prepare an apatite (HA)/PCL composite. It was found that the bone-like apatite formability of PCL was enhanced by PVA coating. The changes of surface properties induced by PVA coating were effective for apatite formation. The apatite formability increased with increasing coating amount. After 24 h incubation, apatite was formed on PVA-coated PCL film but hardly any apatite was found on uncoated PCL plate. The surface chemistry of the specimens was examined using XPS, FT-IR-ATR. The apatite formed was characterized by using SEM, TF-XRD, FT-IR, EDS. The apatite formed was similar in morphology and composition to that of natural bone. This indicated that simple PVA coating on PCL substrate could serve as a novel way to accelerated apatite formation via biomimetic method.     

Synthesis and characterization of superparamagnetic nanoparticles coated with fluorescent gold nanoclusters

Multifunctional nanoparticles (NPs) combining the superparamagnetism of Mn−Zn ferrite and the fluorescence property of gold nanoclusters (NCs) have been prepared by wet chemistry. Magnetic NPs synthesized by co-precipitation method were coated several times with oppositely charged polyelectrolytes (PEs) using the layer-by-layer technique. Common techniques (Fourier transform infrared spectroscopy, electron microscopy, zeta potential, etc.) indicated the monodispersity and the stability of the coated NPs providing a positive charged surface. Fluorescent gold NCs bound to a standard protein bovine serum albumin were adsorbed on the surface of the magnetic NPs. Structural investigations proved the presence of small gold clusters (~2 nm) in a shell surrounding the magnetic nanomaterial. The stable nanocomposite kept the original fluorescence property of the metal clusters with 211-fold increase of the red emission (λ = 690 nm) compared to the uncoated NPs. These NPs can be moved with a permanent magnet despite a 72-wt% increase of the non-magnetic fraction due to the PE coating and the protein adsorption.     

Ultrasound-promoted coating of MOF-5 on silk fiber and study of adsorptive removal and recovery of hazardous anionic dye “congo red”

A metal–organic framework MOF-5 has been synthesized on silk fiber through electrostatic layer-by-layer assembly. The silk surface coating was formed via sequential dipping in an alternating bath of metal and ligand solutions at room temperature by direct mixing. SEM was used to investigate the growth of MOF-5 coating as materials for separation membrane due to their desirable properties in adsorptive removal of congo red (CR) from contaminated water. The adsorption capacity of MOF-5 is remarkable high in the liquid phase. The adsorption of CR at various concentration and contact time in spontaneous process were studied. The silk fibers containing MOF-5 open a wide field of possible applications, such as protection layers or membranes in pollution remediation wastewater and any effluent. Desorption of the dye can be carried out by using NaOH solution with more than about 50% recovery of congo red from MOF-5 coated on silk membrane filtration. In order to investigate the role of sonicating on the morphology of products, one of the reactions was performed with ultrasound irradiation and the crystal growth is completed more than other methods. The samples and adsorption of CR were characterized with SEM, powder X-ray diffraction (XRD) and UV–visible spectroscopy.     

The kinetics of hydrogen (deuterium) sorption by thin palladium layers studied with a piezoelectric quartz crystal microbalance

The kinetics of the hydrogen (deuterium) Sorption processes in the α-phase region of a thin electrodeposited Pd layer (thickness 3 × 10^?5 cm) are reported. Measurements have been performed with a piezoelectric quartz crystal microbalance using an AT-cut crystal with a resonance frequency f⁰_q = 5.27 MHz and a sensitivity of ～10¹⁰ digits g^?1, at a constant temperature 80.3 ± 0.05 °C and different pressures. Both the absorption and the desorption of H₂(D₂) on Pd layers are controlled successively by a chemisorption step (second order kinetics) in the early stage of the processes and by a surface migration step (first order kinetics), in the subsequent stage of the processes. Consistent with the reported piezoelectric quartz crystal microbalance measurements, thermal desorption and electrochemical desorption studies, a mechanism is suggested which takes into account the adsorption ofH(D) atoms on two different surface states: (a) a “pre-dissolved” state which does not depend on the surface nature; (b) and adsorption state, the density of which depends upon the structure and nature of the Pd sample. The kinetic control of the entire processes (sorption and desorption) depends on the ratio of the density of sites (a) to (b).     

Thiolated polyethylene oxide as a non-fouling element for nano-patterned bio-devices

This work describes the synthesis of a thiolated polyethylene oxide that self-assembles on gold to create a non-fouling surface. Thiolated polyethylene oxide was synthesised by reacting 16-mercaptohexadecanoic acid with polyethylene glycol mono methyl ether. The coverage of the thiolated polyethylene oxide on gold was studied by cyclic voltammetry, and the modified surfaces were characterised by X-ray photoelectron spectroscopy and ellipsometry. Protein resistance was assessed using quartz crystal microbalance. Results showed a non-fouling character produced by the thiolated polyethylene oxide. The synthesised product was used as the passivation layer on nano-patterned surfaces consisting of arrayed nano-spots, fabricated by plasma based colloidal lithography. The specific adsorption of anti-bovine serum albumin in the mercaptohexadecanoic acid spots was verified by atomic force microscopy.     

Structural investigation of n-hexadecanoic acid multilayers on mica surface: Atomic force microscopy study

The structure of n-hexadecanoic acid (HA) multilayers formed by spreading an ethanol solution containing this molecule onto a freshly cleaved mica surface has been studied by atomic force microscopy (AFM). AFM images of multilayers obtained with different coating time showed that HA molecules first formed some sporadic domains on mica surface. With the proceeding of the coating process, these domains gradually enlarged and coalesced, until formed a continuous film finally. It was observed that HA molecules were always adsorbed on mica surface with tilted even-numbered layers structure. The height of the repeated tilted bilayer film was measured to be approximately 3.8 ± 0.2 nm, which implied a ∼60° tilt molecular conformation of the HA bilayers on mica surface. Phase image confirmed that the HA multilayers terminated with the hydrophilic carboxylic acid groups. The formation mechanism of the HA multilayers was discussed in detail. Thus, resulted hydrophilic surfaces are of special interest for further study in biological or man-made member systems.     

SPM analysis of fibrinogen adsorption on solid surfaces

The adsorption kinetics, adhesion and orientation of human fibrinogen on solid surfaces have been studied by surface probe microscopy (SPM) and quartz crystal microbalance techniques (QCM). CF₃-, NH₂-terminated organo-silane self-assembled monolayers (SAM) and OH-terminated silicon dioxide have been used as model surfaces. Furthermore, the interaction of fibrinogen with nanocomposite Ti/hydrocarbon plasma polymer films (Ti/ppCH) deposited by dc magnetron sputtering has also been studied.     

Large-area micro/nanostructures fabrication in quartz by laser interference lithography and dry etching

Laser interference lithography (LIL) has the capability to fabricate large-area microstructures on the photoresist with only a couple of minutes’ exposure and development. In this study, LIL was adopted to fabricate micro/nanostructures in quartz by combining the following dry-etching process either reactive ion etching (RIE) or inductively coupled plasma (ICP). A layer of gold film was coated on the quartz to act as a hard mask during the dry-etching process. A microhole array in quartz with a thin gold film covered on the surface was fabricated when choosing RIE. Each hole in the microhole array was surrounded with gold nanoparticle capped silica (Au/SiO₂) cones when using ICP instead of RIE. This is due to the thin gold film that serves as the mask for creating the surface roughness required for creating the silica cone structure.     

Ellipsometry studies of albumin films on tantalum oxide and SiO2

The adsorption of (1) bovine serum albumin in acetate buffer, (2) albumin followed by glutaraldehyde crosslinking, (3) albumin followed by exposure to an albumin/glutaraldehyde solution, and (4) albumin after the surface was subjected to treatment (3), has been studied using Ta oxide/Ta chips and SiO₂/Si wafers as substrates. The films were washed, air dried and measured in air using an automatic laser ellipsometer, 6328 Å. The films formed from treatment (3) and treatment (4) have a lower refractive index and are thicker than films formed from treatment (1) and treatment (2). The adsorption of albumin on SiO₂/Si wafers seems to be slower than that on the Ta oxide/Ta surfaces.     

PMOXA/PAA混合刷用于毛细管电泳在线富集牛血清蛋白

本文发展了一种对蛋白质具有吸附/释放功能的二元混合刷涂层(BBC)毛细管,并将其用于蛋白质的在线富集. 通过阳离子开环聚合可逆加成断裂链转移聚合,分别合成了末端为氨基的聚(2-甲基-2噁唑啉)(PMOXA-NH₂)以及末端为巯基的聚丙烯酸(PAA-SH). 然后通过聚多巴胺黏合层将PMOXA-NH₂和PAA-SH依次接枝到熔融硅毛细管内表面,制备出基于聚(2-甲基-2-噁唑啉)(PMOXA) 和聚丙烯酸(PAA)的BBC毛细管. 利用扫描电镜、X射线光电子能谱分析了在毛细管内表面或毛细管原材料上形成的PMOXA/PAA涂层的厚度及组成. 通过荧光显微镜研究了一定pH及离子强度(I)下,BBC毛细管对蛋白质的吸附/释放功能. 结果表明, pH=5.0 (I=10^-5 mol/L)时,BBC毛细管可以吸附牛血清蛋白(BSA),而当pH=9.0 (I=10^-1 mol/L)时,吸附的BSA可被释放出来. 将这种具有蛋白质吸附/释放功能的涂层管用于毛细管电泳在线富集BSA,以提高BSA的检测灵敏度. 结果表明,在最佳条件下,BSA的灵敏度增强因子超过了5000.     

Composite coating of 58S bioglass and hydroxyapatite on a poly (ethylene terepthalate) artificial ligament graft for the graft osseointegration in a bone tunnel

The purpose of this study was to determine the effect of the combination of hydroxyapatite (HA) and bioglass (BG) on polyethylene terephthalate (PET) artificial ligament graft osseointegration within the bone tunnel. The results of in vitro culturing of MC3T3-E1 mouse osteoblastic cells proved that this HA/BG composite coating can promote the cell compatibility of grafts. A rabbit extraarticular tendon-to-bone healing model was used to evaluate the effect of this composite coating on PET artificial ligaments in vivo. The final results demonstrated that HA/BG coating improved new bone formation at the graft-bone interface and increased the load-to-failure property of graft in bone tunnel compared to the control group at early time. The study has shown that HA/BG composite coating on the PET artificial ligament surface has a positive effect in the induction of artificial ligament osseointegration within the bone tunnel.     

Preparation of graphene-glass fiber-resin composites and its electromagnetic shielding performance

The surface of the glass fiber (GF) was modified by silane coupling agent (KH550) and bovine serum albumin (BSA), and then the graphene oxide (GO) was coated onto the modified surface of the glass fiber. Followed by a reduction reaction, the reduced graphene oxide (RGO) coated on glass fiber was obtained. Finally, the reduced graphene oxide-glass fibers (RGO-GF) were combined with unsaturated resins. The interfacial morphology of reduced graphene oxide-glass fibers was investigated by scanning electron microscopy (SEM). The structure of the materials was analyzed by Fourier transform infrared spectroscopy (FT-IR). The crystal phases of the material were identified by X - ray diffraction (XRD). The mechanical properties and electromagnetic shielding effectiveness of the sample were tested. The results showed that the interface between glass fibers and graphene binds more closely after the glass fibers was treated by KH550. The tensile strength of the RGO-GF composites reached 85.05 MPa. Compared with the GF composites, it increased by 51.4% when the glass fibers content was 30%. The shielding effectiveness of the composites reached 21.3 dB at the frequency range of 8.2–12.4 GHz (x-band). Therefore, by coating the surface with reduced graphene oxide, the glass fibers can make a great shielding effect on the electromagnetic wave.