Effects of gas adsorption on the electrical conductivity of single-wall carbon nanohorns

We present significant electrical conductivity responses of the pelletized as-prepared and oxidized (ox-) single-wall carbon nanohorns (SWNHs) on adsorption of CO(2) and O(2). The morphological and pore structures of both pelletized SWNHs were examined by transmission electron microscopy (TEM) and nitrogen adsorption isotherm, leading to explicit evidences of the formation of nanoscale windows on the wall by oxidation. The SWNH and ox-SWNH induced a semiconducting behavior, strongly responded to CO(2) and O(2) adsorptions, and each exhibited n-type- and p-type-like conductivities. The electrical conductivity increase and decrease for CO(2) and O(2) adsorption, respectively, were observed for SWNH, whereas ox-SWNH showed a marked electrical conductivity drop on CO(2) adsorption and almost no change on O(2) adsorption. The dramatically different electrical conductivity response of ox-SWNH is presumed to be ascribed to the annihilation of pentagons in the single graphene wall by oxidation.     

An electrochemical impedance spectroscopy study of polymer electrolyte membrane fuel cells electrocatalyst single wall carbon nanohorns-supported

Electrochemical impedance spectroscopy (EIS) was used to study the polymer electrolyte membrane fuel cells (PEMFC) performance when using single wall carbon nanohorns (SWNH) to support Pt nanoparticles. Additionally, as-prepared and oxidized SWNH Pt-supports were compared with conventional carbon black. Two different oxidizing treatments were considered: oxygen flow at 500 degrees C and reflux in an acid solution at 85 degrees C. Both oxidizing treatments increased SWNH surface area; oxygen treatment increased surface area 4 times while acid treatment increased 2.6 times. The increase in surface area should be related to the opening access to the inner tube of SWNH. Acid treatment of SWNH increased chemical fragility and decreased electrocatalyst load in comparison with as-prepared SWNH. On the other hand, the oxygen treated SWNH sample allowed to obtain the highest electrocatalyst load. The use of as-prepared and oxygen treated SWNH showed in both cases catalytic activities 60% higher than using conventional carbon black as electrocatalyst support in PEMFC. Moreover, EIS analysis indicated that the major improvement in performance is related to the cathode kinetics in the as-prepared SWNH sample, while concerning the oxidized SWNH sample, the improvements are related to the electrokinetics in both anode and cathode electrodes. These improvements should be related with differences in the hydrophobic character between SWNH and carbon black.     

Use of single wall carbon nanohorns in polymeric electrolyte fuel cells

Single wall carbon nanohorns (SWNH), produced by AC arc discharge in air, were used as Pt and PtRu supports in polymer electrolyte membrane fuel cells (PEMFC). These electrocatalysts were compared with equivalent electrocatalysts supported on commercial carbon back. The SWNH were characterized by differential thermal analysis (DTA), TEM, SEM, and XRD. The produced SWNH were 84.5 wt% pure, containing 3 wt% of amorphous carbon and 12.5 wt% of graphitic carbon. SWNH were used as electrocatalyst supports and tested in the electrodes of two types of polymer electrolyte fuel cells: H₂-fed PEMFC and direct methanol fuel cells (DMFC). The electrocatalyst nanoparticles anchored on both carbon supports were ca. 2.5 nm in diameter obtained by employing ethylene glycol as the reducing agent. The use of SWNH showed catalytic activities 60% higher than using carbon black as the electrocatalyst support in both types of fuel cells.     

Cytotoxicity of BSA‐Stabilized Gold Nanoclusters: In Vitro and In Vivo Study

Gold nanoclusters (Au NCs) are one of the most promising fluorescent nanomaterials for bioimaging, targeting, and cancer therapy due to their tunable optical properties, yet their biocompatibility still remains unclear. Herein, the cytotoxicity of bovine serum albumin (BSA)‐stabilized Au NCs is studied by using three tumor cell lines and two normal cell lines. The results indicate that Au NCs induce the decline of cell viabilities of different cell lines to varying degrees in a dose‐ and time‐dependent manner, and umbilical vein endothelial cells which had a higher intake of Au NCs than melanoma cells show more toxicity. Addition of free BSA to BSA‐Au NCs solutions can relieve the cytotoxicity, implying that BSA can prevent cell damage. Moreover, Au NCs increase intracellular reactive oxygen species (ROS) production, further causing cell apoptosis. Furthermore, N‐acetylcysteine, a ROS scavenger, partially reverses Au NCs‐induced cell apoptosis and cytotoxicity, indicating that ROS might be one of the primary reasons for the toxicity of BSA‐Au NCs. Surprisingly, Au NCs with concentrations of 5 and 20 nM significantly inhibit tumor growth in the xenograft mice model of human liver cancer, which might provide a new avenue for the design of anti‐cancer drug delivery vehicles.     

Gas sensor using single-wall carbon nanohorns

We fabricated a gas sensor using single-walled carbon nanohorns (SWNHs) produced by the gas-injected arc-in-water method. This gas sensor consisted of agglomerated SWNHs as a coating film between Al electrodes on a glass substrate and the shift of the electric resistance of this coating film caused by gas adsorption was monitored. Its sensing property was examined for the detection of NH₃ and O₃ at room temperature. It was confirmed that the electrical resistance of the SWNHs film increases with adsorption of NH₃, whereas the adsorption of O₃ induced the decrease of the resistance. A model to correlate the gas concentration and the sensing property was proposed focusing on the detection of NH₃ based on mono-layer adsorption and a second-order interaction of adsorbed gas molecules for charge transfer.     

Study of Biodistribution of Methotrexate-Loaded Bovine Serum Albumin Nanospheres in Mice

Nanospheres made from natural hydrophilic polymers have been proved efficient in terms of better drug-loading capacity, biocompatibility, and possibility less opsonization by reticuloendothelial system (RES) through an aqueous stearic barrier. Hence, nanospheres containing methotrexate were prepared from bovine serum albumin (BSA) by a novel pH coacervation method. A drug-to-polymer ratio study was carried out to determine the carrier capacity. The batch with the highest drug loading was subjected to in vitro analysis. It was found to provide a slow release after an initial burst release. Biodistribution of nanosphere-bound drug was compared with that of free drug in mice. It was observed that the percentage increase in drug distribution to the lungs, liver, and spleen was markedly high from the nanosphere when compared to free drug.     

Study of biodistribution of methotrexate-loaded bovine serum albumin nanospheres in mice

Nanospheres made from natural hydrophilic polymers have been proved efficient in terms of better drug-loading capacity, biocompatibility, and possibility less opsonization by reticuloendothelial system (RES) through an aqueous stearic barrier. Hence, nanospheres containing methotrexate were prepared from bovine serum albumin (BSA) by a novel pH coacervation method. A drug-to-polymer ratio study was carried out to determine the carrier capacity. The batch with the highest drug loading was subjected to in vitro analysis. It was found to provide a slow release after an initial burst release. Biodistribution of nanosphere-bound drug was compared with that of free drug in mice. It was observed that the percentage increase in drug distribution to the lungs, liver, and spleen was markedly high from the nanosphere when compared to free drug.     

Small-sized carbon nanohorns enabling cellular uptake control

Carbon nanotubes perform well in preclinical tests for drug delivery and diagnostic imaging, but controlling the size at less than 100 nm to avoid nonspecific uptake by reticuloendothelial systems while targeting delivery to cells of interest via receptor-mediated endocytosis is difficult, which currently limits their widespread use. Herein, 20-50-nm graphene tubules, small-sized single-walled carbon nanohorns (S-SWNHs), are obtained with a yield of 20% or higher by an oxidative exfoliation of 100 nm pristine SWNH aggregates. S-SWNHs are highly hydrophilic and remarkably resistant to cellular uptake by macrophages (RAW 264.7 cells), tumor cells (HeLa or KB), or normal cells (FHs 173We). The nonstimulatory property to cell membranes therefore makes cellular uptake control of S-SWNHs by functionalization easy. By attaching phospholipid polyethylene glycol, the cellular internalization of S-SWNHs is almost completely inhibited in RAW 264.7 macrophages. When functionalized with tumor-targeting folic acid (FA), FA-S-SWNHs are taken up by FA receptor-overexpressing KB cells but not by normal human embryonic cells (FHs 173We), which do not express the FA receptor. With a high rate of stealth and targeting in vitro, S-SWNHs are one of the most promising nanoparticles for medical use.     

A TEM study of functionalized magnetic nanoparticles targeting breast cancer cells

In this paper, a transmission electron microscopy (TEM) study was carried out to investigate the ability of magnetic nanoparticles (MNPs) to target breast cancer cells in mice. MNPs were functionalized using Luteinizing Hormone Releasing Hormone (LHRH), whose receptors are expressed in most types of breast cancer cells. LHRH conjugated MNPs (LHRH-MNPs) were injected intravenously into female nude mice bearing MDA-MB-435S.luc tumors for thirty days. These mice were sacrificed 20 h after MNP injection. Tumors and periphery organs including livers, lungs and kidneys were collected for analysis. A dedicated transmission electron microscopy (TEM) study was then carried out to investigate the distribution of nanoparticles in cells. We found that dispersive LHRH-MNPs were distributed in tumor cells and cells in lungs and livers. No LHRH-MNPs were observed in kidney cells. Furthermore, LHRH-MNPs tend to aggregate and form clusters in tumor cells and cells in lungs where metastases were developed. These suggest that MNPs functionalized using LHRH can be used to target both primary cancer cells and the metastatic cells. The study also indicates that TEM is a useful tool to study the sub-cellular distribution of functionalized magnetic nanoparticles in mice bearing breast cancers.     

Evaluation of arsenic trioxide-loaded albumin nanoparticles as carriers: preparation and antitumor efficacy

Bovine serum albumin (BSA) nanoparticles containing arsenic trioxide (As(2)O(3)) were prepared by a pH-coacervation method. To investigate the properties of the As(2)O(3)-loaded BSA nanoparticles, a study on drug-to-polymer ratio was done to determine the drug loading (DL), and a H-600 transmission electron microscope (TEM) was used to examine the particle sizes. The results showed that the DL was 27.8% and the average particle size was about 734 nm. The drug release in vitro test was done, which revealed that the drug release was found to provide a slow release after an initial burst release and the cumulative percentage release reached close to 95%. In vitro cytotoxicity test was carried out using APL NB4 cell lines (acute promyelocytic leukemia), and the anticancer efficacy in vivo against mouse H22 hepatoma cells was evaluated on kungming mice. The results indicated that the anticancer efficacy of the As(2)O(3)-loaded BSA nanoparticles was very obvious.     

Pulmonary Codelivery of Doxorubicin and siRNA by pH‐Sensitive Nanoparticles for Therapy of Metastatic Lung Cancer

A pulmonary codelivery system that can simultaneously deliver doxorubicin (DOX) and Bcl2 siRNA to the lungs provides a promising local treatment strategy for lung cancers. In this study, DOX is conjugated onto polyethylenimine (PEI) by using cis‐aconitic anhydride (CA, a pH‐sensitive linker) to obtain PEI‐CA‐DOX conjugates. The PEI‐CA‐DOX/siRNA complex nanoparticles are formed spontaneously via electrostatic interaction between cationic PEI‐CA‐DOX and anionic siRNA. The drug release experiment shows that DOX releases faster at acidic pH than at pH 7.4. Moreover, PEI‐CA‐DOX/Bcl2 siRNA complex nanoparticles show higher cytotoxicity and apoptosis induction in B16F10 cells than those treated with either DOX or Bcl2 siRNA alone. When the codelivery systems are directly sprayed into the lungs of B16F10 melanoma‐bearing mice, the PEI‐CA‐DOX/Bcl2 siRNA complex nanoparticles exhibit enhanced antitumor efficacy compared with the single delivery of DOX or Bcl2 siRNA. Compared with systemic delivery, most drug and siRNA show a long‐term retention in the lungs via pulmonary delivery, and a considerable number of the drug and siRNA accumulate in tumor tissues of lungs, but rarely in normal lung tissues. The PEI‐CA‐DOX/Bcl2 siRNA complex nanoparticles are promising for the treatment of metastatic lung cancer by pulmonary delivery with low side effects on the normal tissues.     

Modulation of oxidative stress by functionalized fullerene materials in the lung tissues of female C57/BL mice with a metastatic Lewis lung carcinoma

Oxidative stress is considered to be one of the important mechanisms involved in carcinogenesis. To investigate the effect of [Gd@C82(OH)22]n and [C60(OH)20]n nanoparticles on the oxidative stress in the tumor-bearing mice, several antioxidative enzymes and antioxidants were tested for mice with or without tumor inoculation. Transplanted tumors were grown in mice by subcutaneous inoculation of a metastatic Lewis lung carcinoma in female C57/BL mice. More importantly, the tumor cells can metastasize into the normal lung tissues gradually. Therefore, in present paper, the activities of copper-zinc superoxide dismutase (CuZn-SOD), glutathione peroxidase (GSH-Px), glutathione S-transferase (GST), as well as the levels of reduced glutathione (GSH) and malondialdehyde (MDA) in the tumor-invaded lung tissues of the tumor-bearing mice were compared to the nomal lung tissues of normal mice. After treatment with nanoparticles, the activities of GSH-Px and GST and other parameters related to the oxidative stress were downregulated and tended closely to the normal levels. Pulmonary histopathological results also showed that two different types of water-soluble fullerenes can prevent lungs from inflammatory lesion and tumor invasion. These findings indicate two different types of water-soluble fullerenes materials can downregulate the oxidative stress status by scavenging excessive free radicals and inhibiting the lipid peroxidation in tumor-bearing mice, which can partly explain their protective roles on the pulmonary oxidative-damage induced by the tumor metastasis to lung tissues.     

Carbon nanotubes induce secondary structure changes of bovine albumin in aqueous phase

Interaction of nanomaterials to protein molecules is one of the most important issues to deeply understand the influences of the nanomaterials upon physiological processes and protein functions. So far most of investigations focused on the protein molecules adsorbed on the nanomaterials surface, less is known about those in the aqueous phase (not absorbed). In this work, luminescent spectroscopy analysis, circular dichroism measurement, atomic force microscopy, matrix-assisted laser desorption/ionization time of flight mass spectrometry, isoelectric focusing and sulfate polyacrylamide gel electrophoresis were used to investigate the influence of oxidized water-soluble multiwalled carbon nanotubes (CNT) dispersing in aqueous solution upon the structures of bovine serum albumin (BSA) through co-incubation. We focused on BSA molecules that stayed in the aqueous phase instead of those adsorbed by CNT. Experimental results show that the fractions of beta-sheet decreased from 33.3% to 29.8% and beta-turn increased from 2% to 5% in reference with native BSA. There was a slight increase of alpha-helix and a slight reduction of random coil. BSA molecules that had been encountered with CNT and were left in the solution formed a loose and flatten morphology on graphite substrates instead of their native tight and round morphology observed by AFM. The value of isoelectric point for BSA after exposed to CNT moved towards to a higher pH position compared with native BSA. All together, it was concluded that the oxidized water-soluble multiwalled carbon nanotubes not only adsorb bovine serum albumin molecules to their surface, but also induces albumin molecules in the aqueous solution undergo secondary structure changes, which lead to a conformation change.     

Evaluation of Arsenic Trioxide-Loaded Albumin Nanoparticles as Carriers: Preparation and Antitumor Efficacy

Bovine serum albumin (BSA) nanoparticles containing arsenic trioxide (As₂O₃) were prepared by a pH-coacervation method. To investigate the properties of the As₂O₃-loaded BSA nanoparticles, a study on drug-to-polymer ratio was done to determine the drug loading (DL), and a H-600 transmission electron microscope (TEM) was used to examine the particle sizes. The results showed that the DL was 27.8% and the average particle size was about 734 nm. The drug release in vitro test was done, which revealed that the drug release was found to provide a slow release after an initial burst release and the cumulative percentage release reached close to 95%. In vitro cytotoxicity test was carried out using APL NB4 cell lines (acute promyelocytic leukemia), and the anticancer efficacy in vivo against mouse H22 hepatoma cells was evaluated on kungming mice. The results indicated that the anticancer efficacy of the As₂O₃-loaded BSA nanoparticles was very obvious.     

Enhanced antithrombotic effect of hirudin by bovine serum albumin nanoparticles

The aim of this study was to design hirudin-loaded bovine serum albumin (BSA) nanoparticles to control release and improve antithrombotic effect of hirudin. BSA nanoparticles were designed as carriers for delivery of hirudin. Hirudin–BSA nanoparticles were prepared by a desolvation procedure and cross linked on the wall material of BSA. The hirudin–BSA nanoparticles were characterised by particle size distribution, zeta potential, entrapment efficiency, differential scanning calorimetry (DSC), and powder X-ray diffractometry (PXRD). The in vitro release characteristics and pharmacological availability were investigated. The morphology of hirudin–BSA nanoparticles was approximately spherical. The mean particle size was 164.1 ± 5.40 nm and the zeta potential was ?20.41 ± 0.64 mV. The mean entrapment efficiency and drug loading were 85.14% ± 4.79% and 66.38% ± 3.54%, respectively. Results from DSC and PXRD revealed that hirudin in BSA existed in an amorphous state. The release behaviours of hirudin from BSA nanoparticles in phosphate buffer solution were fitted to the bioexponential model. The in vivo result obtained after intravenous injection of hirudin–BSA nanoparticles in normal rats demonstrated that BSA nanoparticles could prolong the antithrombotic effect of hirudin in comparison with hirudin solution. These results suggest that hirudin–BSA nanoparticles may be a promising drug delivery system for thrombosis and disseminated intravascular coagulation therapy.     

Preparation Methods of Biodegradable Microspheres on Bovine Serum Albumin Loading Efficiency and Release Profiles

The solvent evaporation and multiple phase methods for preparing poly-(d, l) lactide microspheres of bovine serum albumin (BSA) were compared. The effects of poly (vinyl alcohol) concentration and external aqueous phase temperature on the loading efficient of BSA microspheres prepared by multiple phase emulsion method were evaluated as well. The BSA loading efficient of microspheres by multiple phase emulsion method was much higher than that by solvent evaporation method. The high aqueous solubility of BSA contributes to the low loading efficieny in the solvent evaporation method, suggesting that this method is inappropriate for proteins with high water solubility. The loading efficieny of microspheres, whcih were prepared by multiple phase emulsion method, increased with PVA concentration but decreased with external aqueous phase temperature. The burst phenomenon of release profiles of microspheres was influenced by poly (vinyl alcohol) concentrations and the external aqueous phase temperature. Considering the duration sustained release, 0.5% w/v of poly (vinyl alcohol) is most appropriate among the concentrations tested for preparing BSA microspheres by multiple phase emulsion method.     

Study on protein conformation and adsorption behaviors in nanodiamond particle-protein complexes

In the present research, the conformation of bovine serum albumin (BSA) in the nanodiamond particle (ND)-BSA complex was studied by Fourier transform infrared spectroscopy, fluorescence spectroscopy, UV-vis spectroscopy, and circular dichroism spectroscopy. The spectroscopic study revealed that most BSA structural features could be preserved in the complex though the BSA underwent conformational changes in the complex due to ND-BSA interaction. In addition, BSA adsorption isotherms and zeta-potential measurements were employed to investigate the pH dependence of the ND-BSA interaction. The changes in surface charge of the ND-BSA complex with pH variations indicated that the binding of BSA to ND might lead to not only the adsorption of BSA onto the ND surface but also the partial breakup of ND aggregates into relatively small ND-BSA aggregates because of the strong binding force between ND and BSA. The results show that ND is an excellent platform for protein immobilization with high affinity and holds great potential to be used for biosensor applications.     

Preparation Methods of Biodegradable Microspheres on Bovine Serum Albumin Loading Efficiency and Release Profiles

The solvent evaporation and multiple phase methods for preparing poly-(d, l) lactide microspheres of bovine serum albumin (BSA) were compared. The effects of poly (vinyl alcohol) concentration and external aqueous phase temperature on the loading efficient of BSA microspheres prepared by multiple phase emulsion method were evaluated as well. The BSA loading efficient of microspheres by multiple phase emulsion method was much higher than that by solvent evaporation method. The high aqueous solubility of BSA contributes to the low loading efficieny in the solvent evaporation method, suggesting that this method is inappropriate for proteins with high water solubility. The loading efficieny of microspheres, whcih were prepared by multiple phase emulsion method, increased with PVA concentration but decreased with external aqueous phase temperature. The burst phenomenon of release profiles of microspheres was influenced by poly (vinyl alcohol) concentrations and the external aqueous phase temperature. Considering the duration sustained release, 0.5% w/v of poly (vinyl alcohol) is most appropriate among the concentrations tested for preparing BSA microspheres by multiple phase emulsion method.     

离子液体双水相中PB与BSA的作用研究

运用荧光光谱,研究了在离子液体双水相体系中吡罗红B(PB)与牛血清白蛋白(BSA)的相互作用。结果表明,在离子液相中PB对BSA产生了荧光猝灭作用,且属于静态猝灭过程。计算得到在298K和308K下的结合常数分别为5.80×105Lomol-1和4.42×105Lomol-1,结合位点数分别为1.18和1.17。热力学参数表明PB与BSA之间的相互作用为静电作用力。用同步荧光法探讨了PB对BSA构象的影响。     

Optimization of the mechanical properties of calcium phosphate/multi-walled carbon nanotubes/bovine serum albumin composites using response surface methodology

Response surface methodology (RSM) coupled with the central composite design (CCD) was used to optimize the mechanical properties of calcium phosphate cement/multi-walled carbon nanotubes/bovine serum albumin (CPC/MWCNTs/BSA) composites. In this study, CPC composites were reinforced by multi-walled carbon nanotubes (MWCNTs) and bovine serum albumin (BSA) in order to induce high mechanical properties in the CPC/MWCNTs/BSA system. The effect of various process parameters on the compressive strength of CPC/MWCNTs/BSA composites was studied using design of experiments (DOE). The process parameters studied were: wt.% of MWCNTs (0.2–0.5 wt.%), wt.% of BSA (5–15 wt.%) and type of MWCNTs (e.g. as-pristine MWCNT (MWCNT-AP), hydroxyl group functionalized MWCNT (MWCNT-OH) and carboxyl group functionalized MWCNT (MWCNT-COOH)). Based on the CCD, a quadratic model was obtained to correlate the process parameters to the compressive strength of CPC/MWCNTs/BSA composites. From the analysis of variance (ANOVA), the most significant factor affected on the experimental design response was identified. The predicted compressive strength after process optimization was found to agree well with the experimental value. The results revealed that at 0.5 wt.% of MWCNT-OH and 15 wt.% of BSA, the highest compressive strength of 14 MPa was obtained.