Enhanced surface activity of activated carbon by surfactants synergism

Activated carbon (AC) modification has been intensively studied in order to design carbon electrodes with enhanced electrochemical performance. Hexadecyltrimethylammonium bromide (HDTMA) and Tween 80 were employed for enhancing the surface activity of AC via synergism. The synergistic effects of the mixed surfactants on AC surface activity in the light of interface behaviors were studied. Both field emission scanning electron micrographs and FTIR spectra indicated a successful adsorption of loaded surfactants. AC gained a good wettability originated from the surfactants, especially in the binary mixture (T80-HDTMA). The zeta potential results unveiled the positive charge density enhancement in the mixed surfactants system. Isoelectric point and point of zero charge implicate heterogeneous distribution of charges and the extent of surfactants treatment. Tween 80 displayed a significant size control dependence on AC particles. Electrochemical characterization revealed a higher specific capacitance and a decaying resistance of specific capacitance in AC-T80-HDTMA than AC-HDTMA at high concentration. In 5 g L⁻¹ of NaCl, AC-T80-HDTMA (0.01 : 0.01 mM) exhibits the specific capacitance of 209.79 F g⁻¹, at 0.8 V whereas AC-HDTMA (0.01 mM) and AC exhibited 186.5 F g⁻¹, 178.9 F g⁻¹, respectively. Moreover, the stability testing reveals a strong attachment of HDTMA in AC-T80-HDTMA than AC-HDTMA with the loss of 0.32% and 1.32%, respectively. The hypothetical synergistic mechanism of surfactants adsorption on the surface of AC was depicted as hydrophobic interaction and steric stabilization being the main keys for the synergy between cationic and nonionic surfactants. This study demonstrates the beneficial effects of mixed surfactants on AC electrode properties and discloses the impact on electrochemical performance.

Enhancement of AC surface activity by surfactants synergism for electrochemical applications.     

Enhanced catalytic activity of inhomogeneous Rh-based solid-solution alloy nanoparticles

Catalytic Rh-based alloy nanoparticles (NPs) with inhomogeneous solid-solution structures were prepared from homogeneous solid-solution alloy NPs. Compared with homogeneous alloy NPs, these inhomogeneous alloy NPs exhibited enhanced catalytic activity and superior catalytic durability. Homogeneous solid-solution alloy NPs consisting of Rh and other immiscible noble metals were synthesized by laser-induced nucleation method in metallic ion solutions. STEM elemental mapping and EDS composition analysis of the particles clearly demonstrated that all the constituents were uniformly dispersed within the NPs. Moreover, the compositions of the alloys were nearly identical to the initial feeding ratios of metallic ions in the mixed solutions, strongly indicating the formation of equimolar solid-solution alloy NPs over the entire composition range. Although the catalytic stability of these Rh-based homogeneous alloy NPs during CO oxidation was improved, their catalytic activity was comparable to that of pure metal catalysts, owing to the uniform local structure at the atomic level. However, the catalytic activity of the alloy NPs was enhanced by heat treatment, which introduced inhomogeneity in the atomic distribution within the NPs. The enhanced activity was due to dissimilar interfaces in the inhomogeneous solid-solution alloy NPs.

Catalytic Rh-based alloy nanoparticles (NPs) with inhomogeneous solid-solution structures were prepared from homogeneous solid-solution alloy NPs.     

Enhanced osteogenic differentiation of BMSCs and M2-phenotype polarization of macrophages on a titanium surface modified with graphene oxide for potential implant applications

Osseointegration at the bone–implant interface is a complex biological process that is triggered by the immune-inflammatory response and mediated by various cell types such as, bone-forming cells and immune cells, especially macrophages. The polarization of macrophages to inflammatory/regenerative (M1/M2) phenotypes, as well as the osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs) at the bone–implant interface, significantly affects implant osseointegration and even causes implant failure. Graphene oxide (GO) is a promising candidate for performing implant surface functionalization to modulate the interactions between implants and cells. Herein, we explored the effects of a GO coating on the osteogenic differentiation of BMSCs and the polarization of macrophages to enhance the application of GO surface modification in improving bone–implant integration. In the present study, a large particle sandblasting and acid etching (SLA) surface that is commonly used in clinical practice was selected as the control group, and GO was deposited on the SLA surface by the ultrasonic atomization spraying technique. The surface characteristics of these two groups, including the surface morphology, roughness, wettability, protein adsorption capacity and cell compatibility, were assessed. Then, the effects of GO surface modification on the osteogenic differentiation of BMSCs and the polarization of macrophages were evaluated. The results showed that the GO coating was successfully fabricated on the titanium substrates, which endowed the SLA surface with improved hydrophilicity and protein adsorption capacity and reduced roughness. Compared with the SLA surface, the GO-modified surface significantly enhanced the osteogenic differentiation of BMSCs and the M2-phenotype polarization of macrophages in vitro. This dual-regulatory role is of great significance in achieving rapid osseointegration as well as resolving the poor osseointegration associated with macrophage-related inflammation.

Dual roles of graphene oxide modification for enhancing osteogenic differentiation of BMSCs and M2-phenotype polarization of macrophages.     

Influence of surface treatment on PEDOT coatings: surface and electrochemical corrosion aspects of newly developed Ti alloy

Surface treatment of metallic materials prior to the application of polymer coatings plays an important role in providing improved surface features and enhanced corrosion protection. In the current investigation, we aimed to evaluate the effect of surface treatment of newly developed TiNbZr (TNZ) alloys on the surface characteristics, including the surface topography, morphology, hydrophobicity and adhesion strength of subsequent poly(3,4-ethylenedioxythiophene) (PEDOT) coatings. The surface morphology, chemical composition, and surface roughness of both treated and coated alloys were characterized by scanning electron microscopy, energy dispersive spectroscopy, and optical profilometry, respectively. The adhesion strength of the coating was measured using a micro scratch machine. Furthermore, we also evaluated the performance of electrochemically synthesized PEDOT coatings on surface-treated TNZ alloys in terms of the surface protective performance in simulated body fluid (SBF) and in vitro bioactivity in osteoblast MG63 cells. Surface analysis findings indicated that the nature of the PEDOT coating (surface morphology, topography, wettability and adhesion strength) was intensely altered, while the surface treatment performed before electrodeposition facilitated the overall performance of PEDOT coatings as implant coating materials. The obtained corrosion studies confirmed the enhanced corrosion protection performance of PEDOT coatings on treated TNZ substrates. In vitro cell culture studies validated the improved cell adhesion and proliferation rate, further highlighting the important role of surface treatment before electrodeposition.

Surface treatment of metallic materials prior to the application of polymer coatings plays an important role in providing improved surface features and enhanced corrosion protection.     

Enhanced catalytic activity and thermal stability of lipase bound to oxide nanosheets

The present study reports the effects of binding of lipase, which is an inexpensive digestive enzyme (candida antarctica lipase) that catalyzes the hydrolysis reaction and is frequently utilized for artificial synthesis of a variety of organic molecules, to titanate nanosheets (TNSs) on their biocatalytic activities and stabilities under several lipase concentrations. TNSs were prepared through a hydrolysis reaction of titanium tetraisopropoxide (TTIP) with tetrabutylammonium hydroxide (TBAOH), resulting in formation of a colorless and transparent colloidal solution including TNSs with nanometric dimensions (hydrodynamic diameter: ca. 5.6 nm). TNSs were bound to lipase molecules through electrostatic interaction in an aqueous phase at an appropriate pH, forming inorganic-bio nanohybrids (lipase–TNSs). The enzymatic reaction rate for hydrolysis of p-nitrophenyl acetate (pNPA) catalyzed by the lipase–TNSs, especially in diluted lipase concentrations, was significantly improved more than 8 times as compared with free lipase. On the other hand, it was confirmed that heat tolerance of lipase was also improved by binding to TNSs. These results suggest that the novel lipase–TNSs proposed here have combined enhancements of the catalytic activity and the anti-denaturation stability of lipase.

The present study reports the preferable effects of binding of lipase to titanate nanosheets. The binding largely enhanced biocatalytic activity and thermal stability of lipase especially at diluted concentrations.     

Bone marrow stromal cells enhance the osteogenic properties of hydroxyapatite scaffolds by modulating the foreign body reaction

We aimed to investigate the osteogenic properties of bone marrow stromal cell (BMSC)‐loaded biomimetic constructs composed of hydroxyapatite (HA), with or without in vitro cell‐derived extracellular matrix (HA‐ECM), and to assess the cellular components of the elicited foreign body reaction. HA‐ECM constructs were produced by adult rat dermal fibroblasts cultured on top of synthetic HA microparticles. Rat calvarial critical‐sized defects (8 mm) were created and treated with the generated HA‐ECM constructs or HA microparticles, alone or combined with green fluorescent protein (GFP)‐expressing BMSCs. The new bone formation and the local cellular inflammatory response (macrophages, neutrophils, lymphocytes, eosinophils and PCNA‐index) were assessed by histomorphometry and immunohistochemistry at 2 and 12 weeks postoperatively. In addition, the BMSCs' survival and engraftment were checked. The largest volume of the newly formed bone was found in defects treated with HA‐ECM constructs combined with BMSCs (p < 0.05). Moreover, the implanted BMSCs modulated the local inflammatory response, demonstrated by either a significant increase (HA vs HA + BMSCs) or decrease (HA‐ECM vs HA‐ECM + BMSCs) of the inflammatory cell number. No donor BMSCs were detected at the site of implantation or in the host bone marrow at 2 or 12 weeks postoperatively. In conclusion, the treatment of critical‐sized calvarial defects with the BMSC‐loaded biomimetic constructs has significantly enhanced bone repair by modulating the foreign body reaction. Our findings highlight the implications of BMSCs in the regulation of the foreign body reaction triggered by tissue‐engineered constructs, proving a higher efficiency for the BMSC combination therapy. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhanced photoluminescence of potassium-doped tungsten oxide by acetone exposure

Studies of optical properties of doped nanocrystals of tungsten trioxide can elucidate new information about the material. A novel molecule-enhanced photoluminescence (PL) of potassium-doped tungsten trioxide (K_xWO) was explored in the presence of different gases to understand charge transfer between molecules and K_xWO on the properties of the material. We performed Raman spectroscopy and PL experiments in the presence of gaseous acetone or ethanol mixed with other gases (N₂ and O₂). PL at 630 nm from K_xWO was observed and further enhanced when the sample was continuously irradiated with a 532 nm CW laser in acetone. A mechanism of strong emission of the PL induced by the charge transfer between the acetone and the K_xWO is proposed.

Studies of optical properties of doped nanocrystals of tungsten trioxide can elucidate new information about the material.     

Neodymium-decorated graphene oxide as a corrosion barrier layer on Ti6Al4V alloy in acidic medium

Ti6Al4V alloy is light weight and is used in construction, oil industries and airbus, automobile, and bio implant materials. The native oxide layers of the alloy are not stable at high temperatures and strong mineral acid environments. The conventional epoxy-based layers are porous and the alloy finally fails in the harsh environment in the long term. Therefore, the carbon-based functional materials are being proposed as coating materials to overcome the alloy degradation. In the present contribution, we have used the neodymium-decorated graphene oxide as the corrosion inhibiting barrier for the Ti6Al4V alloy. As a novelty, we found that the few-layer graphene decorated with neodymium acts as a self-cleaning coating. The Nd-decorated graphene oxide were studied by XRD, TEM, FESEM, FTIR, UV, and Raman spectroscopy. The corrosion inhibition efficiency was studied by electrochemical methods.

Neodymium-decorated graphene oxide is chemisorbed by non-bonding electrons on Ti6Al4V surface increasing the corrosion inhibition in acidic media.     

A facile chemical synthesis of nanoflake NiS2 layers and their photocatalytic activity

A single-phase and crystalline NiS₂ nanoflake layer was produced by a facile and novel approach consisting of a two-step growth process. First, a Ni(OH)₂ layer was synthesized by a chemical bath deposition approach using a nickel precursor and ammonia as the starting solution. In a second step, the obtained Ni(OH)₂ layer was transformed into a NiS₂ layer by a sulfurization process at 450 °C for 1 h. The XRD analysis showed a single-phase NiS₂ layer with no additional peaks related to any secondary phases. Raman and X-ray photoelectron spectroscopy further confirmed the formation of a single-phase NiS₂ layer. SEM revealed that the NiS₂ layer consisted of overlapping nanoflakes. The optical bandgap of the NiS₂ layer was evaluated with the Kubelka–Munk function from the diffuse reflectance spectrum (DRS) and was estimated to be around 1.19 eV, making NiS₂ suitable for the photodegradation of organic pollutants under solar light. The NiS₂ nanoflake layer showed photocatalytic activity for the degradation of phenol under solar irradiation at natural pH 6. The NiS₂ nanoflake layer exhibited good solar light photocatalytic activity in the photodegradation of phenol as a model organic pollutant.

A single phase nanoflake NiS₂ layer synthesized by a facile chemical bath deposition showed good solar light photocatalytic degradation of phenol with good stability and reusability.     

Changes in the surface activity of bronchoalveolar washings and their cellular composition in bronchial asthma

The superficial activity and cytological composition of bronchoalveolar washes off (BAW) were investigated in 55 patients with bronchial asthma. As compared to the control group the patients with bronchial asthma in remission demonstrated a moderate decrease in the superficial BAW activity which grew in the phase of exacerbation, a degree of variations of the superficial BAW activity depending on the expression of exacerbation. Correlation between a decrease in the superficial BAW activity and changes in an endopulmonary cytogram was found. On the 25th day of the treatment of the patients with bronchial asthma at the Tuya-Ashu mountain pass (Tien Shan, 3200 m above the sea level) under the conditions of mountain climate superficially active BAW properties and edopulmonary cytogram got back to normal.     

Optimizing graphene oxide membranes for effective removal of dyes by modulating the reduction degree and doped nitrogen

The excellent mechanical and chemical characteristics of graphene oxide (GO) enable their potential application in the realm of membrane separation. However, the expansion and instability of GO nanosheets in water limit its application. In this work, nitrogen-doped GO (NGO) was obtained by a harmless hydrothermal reduction method. The obtained NGO films were attached to a polyvinylidene fluoride support membrane by vacuum filtration. By changing the hydrothermal reaction temperature, the reduction degree of GO and doping amount of nitrogen was adjusted to control the inter-layer structure and permeability of NGO. The defect of NGO nanosheets and the reduction of oxygen-containing functional groups could accelerate the transportation of water molecules through the inter-layer space of the hydrophobic graphene sheets. Significantly, the polarization and high adsorption energy of pyridine-N serve as a supplement to the exclusion mechanism of the inter-layer spacing. NGO membranes have better permeability than the initial GO membranes without sacrificing the rejection rate. The optimized NGO film has a significant rejection rate of above 99% for various dyes, such as methylene blue, Congo red and methyl blue.

The defect of NGO nanosheets and the reduction of oxygen-containing functional groups could accelerate the transportation of water molecules through the inter-layer space of the hydrophobic graphene sheets.     

Enhanced transfection efficiency of PAMAM dendrimer by surface modification with L-arginine.

We designed a novel type of arginine-rich dendrimer, with a structure based on the well-defined dendrimer, polyamidoamine dendrimer (PAMAM). Further characterization was performed to prove that the polymer is a potent nonviral gene delivery carrier. The primary amines located on the surface of PAMAM were conjugated with L-arginine to generate an L-arginine-grafted-PAMAM dendrimer (PAMAM-Arg). For comparison, an L-lysine-grafted-PAMAM dendrimer (PAMAM-Lys) was also generated and compared as a control reagent. The polymers were found to self-assemble electrostatically with plasmid DNA, forming nanometer-scale complexes. From dynamic light scattering experiments, the mean diameter of the polyplexes was observed to be around 200 nm. We used PicoGreen reagent as an efficient probe for assaying complex formation of polymers with plasmid DNA. The complex composed of PAMAM-Arg/DNA showed increased gene delivery potency compared to native PAMAM dendrimer and PAMAM-Lys. The cytotoxicity and transfection efficiencies for 293, HepG2, and Neuro 2A cells were measured by comparison with PEI and PAMAM. In addition, transfection experiments were performed in primary rat vascular smooth muscle cells, and PAMAM-Arg showed much enhanced transfection efficiency. These findings suggest that the L-arginine-grafted-PAMAM dendrimer possesses the potential to be a novel gene delivery carrier for gene therapy.     

Enhanced nitric oxide concentrations and expression of nitric oxide synthase in acupuncture points/meridians

OBJECTIVES: The objectives of this study were to examine the distributions of nitric oxide (NO) in the skin points (acupoints)/meridian regions and determine whether neuronal nitric oxide synthase (nNOS) protein levels were associated with NO concentrations in the areas. DESIGN: Low skin resistance points (LSRP) on the skin surface in response to electrical stimuli were performed in anesthetized adult rats. The skin together with subcutaneous tissue was isolated in meridian regions from PC 2 to 6, BL 36 to 57, CV 3 to 22, and GV 2 to 14. Control skin tissues were obtained in the areas close to related meridians without containing LSRP. Concentrations of nitrite (NO(2)(-)), nitrate (NO(3)(-)), and total NO(2)(-) plus NO(3)(-) (NO(x)(-)) were quantified in the skin tissues, micropunches of brain nuclei, and blood vessels in a blinded fashion. Western blots were also conducted using polyclonal anti-nNOS and anti-endothelial nitric oxide synthase (eNOS) antibody in the skin tissues. RESULTS: NO(x)(-) and NO(3)(-) concentrations were higher (45 +/- 8% and 43 +/- 7% in the CV, 47 +/- 7% and 51 +/- 9% in the BL, and 47 +/- 8% and 45 +/- 6% in the PC) than those in control regions (p < 0.05, n = 6). NO(x)(-) concentrations are 2- to 3-fold greater in skin tissues than those in brain regions and blood vessels (p < 0.05, n = 6-8). nNOS protein levels were consistently increased in the skin regions of BL, PC, and GV meridians compared with their controls (p < 0.05, n = 5-7) but endothelial NO synthase expression was not changed. CONCLUSION: This is the first evidence showing that NO contents and nNOS expression are consistently higher in the skin acupoints/meridians associated with low electric resistance. The results suggest that enhanced NO in the acupoints/meridians is generated from multiple resources including neuronal NOergic system, and NO might be associated with acupoint/meridian functions including low electric resistance.     

Enhanced demonstration of cell surface immunoglobulins in paraffin-processed tissue

A review of immunohistology, involving the more commonly encountered fixation protocols and the use of proteolytic agents, was undertaken in an attempt to establish a method whereby cell surface immunoglobulins could be reliably demonstrated in routinely processed paraffin tissue sections. Immunoglobulin D (IgD) was selected as a suitable antigen for detection in reactive lymphoid tissues, since it is known to be present both on the cell surface and in the cytoplasm. Using the indirect immunoperoxidase technique and the alkaline phosphatase/anti-alkaline phosphatase technique as standard methods, only cytoplasmic IgD was identifiable in paraffin sections with monoclonal antibodies. However, using polyclonal antisera a technique was established in which membrane-bound IgD was also demonstrated in paraffin sections.     

骨科植入物表面抗感染修饰及其骨整合性的研究进展

植入物相关感染和无菌性松动是导致内固定或关节假体失效的最主要原因,已然成为了骨科医师亟待解决的难题。一个理想的骨科植入物需要同时具备良好的抗菌性与骨整合特性,从而取得长期稳定的内固定效果。本文从该点出发,综合了国内外在植入物表面抗感染修饰研究领域的最新进展,着重总结与阐述了目前植入物表面抗感染修饰的最新策略,同时对促进植入物表面骨整合的相关策略进行了综述,为今后的研究提供了新的思路。     

Role of chemotactic factor inactivator in modulating alveolar macrophage-derived neutrophil chemotactic activity

The stimulated alveolar macrophage is a potent source of neutrophil chemotactic activity. The release of this chemotactic activity can be inhibited by pretreating alveolar macrophages with anti-C5 antibody. We hypothesized that C5a, a fragment cleaved from C5 when C5 is activated, might activate the alveolar macrophage to release neutrophil chemotactic activity and that chemotactic factor inactivator, a serum inhibitor of C5a, could decrease this release. Activated complement components including C5a were found to stimulate guinea pig macrophages to release chemotactic activity into their culture supernatants at levels that were significantly higher than the chemotactic activity of C5a alone (P less than 0.001). Chemotactic factor inactivator was found to cause a marked reduction in the chemotactic activity released by macrophages stimulated with phagocytic and nonphagocytic stimuli (P less than 0.001, all comparisons). These data indicate that C5a can stimulate alveolar macrophages to release chemotactic activity in vitro, and that chemotactic factor inactivator may play a role in modulating this process.     

Enhanced fungicidal activity of N-chlorotaurine in nasal secretion

The antifungal activity of N-chlorotaurine (NCT), a long-lived oxidant produced by stimulated human leucocytes, was investigated. Incubation of Aspergillus spp., Candida spp., Fusarium spp., Penicillium spp. and Alternaria spp. in 1% NCT (55 mM) for 1-4 h produced a log10 reduction in cfu of between 1 and 4. In samples of nasal secretion, killing was significantly hastened (30 min), which may be explained by the formation of monochloramine by halogenation of ammonium, which was found at a concentration of 1 mM in these samples. For these reasons, NCT is of interest as a new agent for treatment of local inflammatory mycosis, e.g. eosinophilic fungal rhinosinusitis.     

The role of surface reduction in the formation of Ti interstitials

Density functional theory simulations are used to investigate the formation and mobility of Ti interstitial ions, Ti_i, at the (110) surface of rutile TiO₂. Interstitials were found to be favoured in the second layer below the surface plane, where they induce electron polaron states at surface and subsurface lattice Ti atoms. Reduction of the surface significantly lowers the barrier for Ti_i formation at the surface: the barrier for formation of Ti_i is reduced to just ∼0.5 eV for a Ti atom next to two bridging oxygen vacancies. However, the barrier to separate the interstitial from the surface oxygen vacancies is ∼2.5 eV. The bulk diffusion barrier is recovered after the interstitial is moved away from the vacancy complex. These results support an experimentally postulated mechanism of Ti_i formation and contribute to our understanding of the TiO₂ surface reduction and reoxidation.

Density functional theory simulations are used to investigate the formation and mobility of Ti interstitial ions, Ti_i, at the (110) surface of rutile TiO₂.     

Enhanced circulation time and antitumor activity of doxorubicin by comblike polymer-incorporated liposomes

Polymer incorporation on liposomal membranes has been extensively studied as a method of enhancing the circulation time of liposomes in the bloodstream. In this study, we investigated the in vitro and in vivo characteristics of liposomes whose surface was modified using a comblike polymer comprised of a poly(methyl methacrylate) (PMMA) backbone and short poly(ethylene oxide) (PEO) side chains. Doxorubicin (DOX)-loaded liposomes incorporating with the comblike polymer were prepared and their circulation time, biodistribution and antitumor activity were evaluated in B16F10 melanoma tumor-bearing mice. The circulation half-life time in the bloodstream of the comblike polymer-incorporated liposomes (CPILs) was approximately 14- or 2-fold higher than those of the conventional or polyethyleneglycol-fixed liposomes (PEG-liposomes), respectively. Additionally, in the biodistribution assay, the accumulation of the CPILs in the tumor was higher than those of the other liposomes. Based on this result, the antitumor activities of the CPILs were higher than those of conventional liposome formulation of DOX or free DOX due to the higher passive targeting efficiency of the long-circulating CPILs to tumor. This study suggests that the incorporation of the comblike polymer on the liposomal membrane is a promising tool to further improve circulation time of liposomes in tumor-bearing mice.