Preparation and characterization of a novel organic-inorganic nanohybrid "cerasome" formed with a liposomal membrane and silicate surface

A novel class of organic-inorganic hybrids, the so-called cerasomes, which have a bilayer vesicular structure and a silicate surface, has been synthesized by combination of sol-gel reaction and self-assembly of organoalkoxysilanes with a molecular structure analogous to lipids. We have synthesized two cerasome-forming organoalkoxysilanes, N-[N-(3-triethoxysilyl)propylsuccinamoyl]dihexadecylamine (1) and N,N-dihexadecyl-N (alpha)-[6-[(3-triethoxysilyl)propyldimethylammonio]hexanoyl]glycinamide bromide (2), and investigated the synthetic conditions of the cerasomes and their structural characteristics. For the proamphiphilic 1, the cerasome was obtained under restricted pH conditions where acid-catalyzed hydrolysis of the triethoxysilyl moiety proceeded without disturbing the vesicle formation. In contrast, the amphiphilic 2, additionally having a hydrophilic quaternary ammonium group, formed stable dispersions of the cerasome in a wide pH range. The hydrolysis behavior of the triethoxysilyl groups was monitored by (1)H NMR spectroscopy. Morphology of the cerasomes having the liposomal vesicular structure was confirmed by TEM observations. Extent of the development of siloxane networks through condensation among the silanol groups on the cerasome surface was evaluated by using MALDI-TOF-MS spectrometry. Formation of oligomers of the cerasome-forming lipids in the vesicle was clearly confirmed. Due to the siloxane network formation, the cerasome showed remarkably high morphological stability compared with a reference liposome, as evaluated by surfactant dissolution measurements.     

Design and Synthesis of Lipidic Organoalkoxysilanes for the Self‐Assembly of Liposomal Nanohybrid Cerasomes with Controlled Drug Release Properties

This paper reports the facile design and synthesis of a series of lipidic organoalkoxysilanes with different numbers of triethoxysilane headgroups and hydrophobic alkyl chains linked by glycerol and pentaerythritol for the construction of cerasomes with regulated surface siloxane density and controlled release behavior. It was found that the number of triethoxysilane headgroups affected the properties of the cerasomes for encapsulation efficiency, drug loading capacity, and release behavior. For both water‐soluble doxorubicin (DOX) and water‐insoluble paclitaxel (PTX), the release rate from the cerasomes decreased as the number of triethoxysilane headgroups increased. The slower release rate from the cerasomes was attributed to the higher density of the siloxane network on the surface of the cerasomes, which blocks the drug release channels. In contrast to the release results with DOX, the introduction of one more hydrophobic alkyl chain into the cerasome‐forming lipid resulted in a slower release rate of PTX from the cerasomes due to the formation of a more compact cerasome bilayer. An MTT viability assay showed that all of these drug‐loaded cerasomes inhibited proliferation of the HepG2 cancer cell line. The fine tuning of the chemical structure of the cerasome‐forming lipids would foster a new strategy to precisely regulate the release rate of drugs from cerasomes.     

Cerasomes: Soft Interface for Redox Enzyme Electrochemical Signal Transmission

Anionic cerasomes, which consist of a liposomal lipid bilayer and a ceramic surface, were used as a soft interface for the construction of an integrated modified electrode to achieve the transmission of chemical information from a redox enzyme through electrical signals. The morphological properties of the cerasomes were systematically compared with those of two structural analogues, namely, liposomes and silica nanoparticles. The results indicated that the cerasomes combined the advantages of liposomes and silica nanoparticles. The lipid bilayer gave excellent biocompatibility, as in the case of liposomes, and high structural stability, similar to that of silica nanoparticles, was derived from the silicate framework on the cerasome surface. The performance at the electrochemical interface created by means of a combination of cerasomes and horseradish peroxidase on a glassy carbon electrode was much better than those achieved with liposomes or silica nanoparticles instead of cerasomes. The potential use of cerasomes in the construction of supramolecular devices for mediator‐free biosensing was evaluated.     

Encapsulation of Quantum Dots Inside Liposomal Hybrid Cerasome Using a One-Pot Procedure

A one-pot strategy for the fabrication of the quantum dots loaded cerasome has been successfully developed based on the condensation of dihexadecylamine and 3-isocyanatopropyltriethoxysilane, followed by spontaneous encapsulation and solubilization of hydrophobic quantum dots into the hybrid liposomal cerasomes in combination of self-assembly and sol-gel process. Fourier transform infrared spectroscopy and mass spectra prove the formation of the intermediate organoalkoxysilane with a lipid-like structure, which forms cerasome vesicles. After encapsulation into cerasome, quantum dots become well dispersed in aqueous solution. Such water-soluble QD cerasomes exhibit a better photostability and retain the luminescence property of the original hydrophobic quantum dots.     

Sol–gel nanohybrid materials prepared via supramolecular organization

This article reports on recent progress in the synthesis of sol–gel nanohybrid materials based on the supramolecular organization. A variety of nanohybrid materials has been obtained by molecular design of the precursors and systematical control of synthetic processes. Organoalkoxysilanes with covalently attached hydrophobic tails are hydrolyzed to form amphiphilic molecules containing silanol groups, leading to the formation of vesicular structures. The obtained hybrid has analogous structures of both cell membrane and silica particle and was named “cerasome”. The cerasome can achieve the hierarchical three-dimensional organization of vesicular particles on the substrate. The nanohybrids are developed not only by the hydrophobic interaction of amphiphilic molecules but also by the electrostatic interaction. The layer-by-layer (LbL) assembly of the water-soluble titania precursor with polycation is adopted for nanohybrid coatings containing titania nanoparticles on the substrates. In addition, preparation of hybrid hollow capsules via LbL assembly and sol–gel method with colloid templating is also discussed.     

Recent advances in liposomal nanohybrid cerasomes as promising drug nanocarriers

Liposomes have been extensively investigated as possible carriers for diagnostic or therapeutic agents due to their unique properties. However, liposomes still have not attained their full potential as drug and gene delivery vehicles because of their insufficient morphological stability. Recently, a super-stable and freestanding hybrid liposomal cerasome (partially ceramic- or silica-coated liposome) has drawn much attention as a novel drug delivery system because its atomic layer of polyorganosiloxane surface imparts higher morphological stability than conventional liposomes and its liposomal bilayer structure reduces the overall rigidity and density greatly compared to silica nanoparticles. Cerasomes are more biocompatible than silica nanoparticles due to the incorporation of the liposomal architecture into cerasomes. Cerasomes combine the advantages of both liposomes and silica nanoparticles but overcome their disadvantages so cerasomes are ideal drug delivery systems. The present review will first highlights some of the key advances of the past decade in the technology of cerasome production and then review current biomedical applications of cerasomes, with a view to stimulating further research in this area of study.     

Heavy metal removal with magnetic coffee grain

The presence of heavy metals in environmental waters having an important place in the industrial waste is a major threat to viability. Heavy metals are transported to humans through the ecological cycle, damaging many tissues and organs. In recent years, agricultural and food waste can be used to remove heavy metals. At the present study, magnetically modified coffee grains which are alternative to conventional particle systems were prepared and heavy metal removal performances were investigated. The coffee grains used were magnetically modified by contact with water-based magnetic fluid. Magnetically modified coffee grains were characterized by scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area analysis and electron spin resonance (ESR). Adsorption studies are made with four different heavy metal ions, namely Cu(II), Pb(II), Cd(II) and Zn(II). Adsorption isotherms were determined and heavy metal removal performance of magnetic coffee grains were investigated from synthetic waste water.     

Surface molecularly imprinted magnetic microspheres for the recognition of albumin

A new approach, combining metal coordination with the molecular imprinting technique, was developed to prepare affinity materials. Magnetic poly(glycidyl methacrylate) microspheres in monosize form were used for specific recognition toward the target protein. The magnetic poly(glycidyl methacrylate) microspheres were prepared by dispersion polymerization in the presence of magnetite nanopowder. Surface imprinted magnetic poly(glycidyl methacrylate) microspheres based on metal coordination were prepared and used for the selective recognition of human serum albumin. Iminodiacetic acid was used as the metal coordinating agent and human serum albumin was anchored by Cu²⁺ ions on the surface of magnetic poly(glycidyl methacrylate) microspheres by metal coordination. The magnetic poly(glycidyl methacrylate) microspheres were coated with a polymer formed by condensation of tetraethyl orthosilicate and 3‐aminopropyltrimethoxysilane. The human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres were characterized by scanning electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy and particle size analysis. The maximum adsorption capacity of human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres was 37.7 mg/g polymer at pH 6.0. The selectivity experiments of human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres prepared with different concentrations in the presence of lysozyme, bovine serum albumin and cytochrome C were performed in order to determine the relative selectivity coefficients.     

Coaxial metal and magnetic alloy nanotubes in polycarbonate templates by electroless deposition

We present a novel technique for the preparation of coaxial metal and magnetic alloy nanotubes, which is demonstrated for the coaxial nanotubes of Ni/Co and Ni/CoNiFe alloys deposited in activated polycarbonate templates using electroless plating. For each metal or alloy the tube wall thickness was controlled to be less than 100 nm. The process involved two consecutive deposition steps from hypophosphite and/or borane reducing agent based electroless plating solutions. We further characterise the magnetic properties of the ternary magnetic alloy films and coaxial nanotubes. The coaxial tubes show homogenous wall thickness and composition, which is delineated from the magnetic measurements.     

Preparation and characterization of a novel nanocomposite: silver nanoparticles decorated cerasome

In this study, a novel artificial hybrid vesicle, nano silver particles decorated cerasome were fabricated through sol–gel and self-assemble methods as well as in situ reduction. Samples were characterized in terms of hydrodynamic size and surface morphology via dynamic light scattering as well as scanning and transmission electron microscopies. Analysis through energy dispersive X-ray spectrometer proved the existence of silver particles. Due to the high morphological stability of cerasome, Silver nanoparticles with a size of about 5–10 nm can be deposited on the surface without any stabilizers. The UV spectra revealed a single symmetric extinction peak at 406 nm, confirming the spherical shape of the synthesized silver nanoparticles. Several reducing agents were screened before confirming sodium borohydride (NaBH₄). Comparison of different NaBH₄/lipid ratios (K_{NaBH4/cerasome-forming lipid}) was then carried out in order to ascertain its effect. Investigation of the stability of this hybrid vesicles was carried out, indicating that it can be stored at 4 °C for at least 3 months without any morphological change. Results demonstrated that this hybrid vesicle has excellent morphological stability, which impart it significant potential for various applications such as being an antibacterial material and a radio sensitization agent.     

石墨烯对镍钛形状记忆合金耐腐蚀性能的影响

利用化学气相沉积法在镍钛形状记忆合金表面原位生长出石墨烯,拟提高镍钛形状记忆合金的抗腐蚀性能。通过X射线光电子能谱、拉曼光谱与扫描电镜等手段对其表征,分析石墨烯修饰后的合金表面结构和形貌。在人工唾液环境中探究了石墨烯对镍钛形状记忆合金的腐蚀速率、细胞毒性和金属释放的影响。结果表明,石墨烯在金属基体和腐蚀介质之间可以起到物理屏蔽作用,可明显地降低金属基体发生腐蚀的速率,对镍钛合金具有较强的保护能力。     

FeCo/C nanocomposites: Synthesis,magnetic and electromagnetic properties

FeCo alloy nanoparticles encapsulated in the carbon matrix of metal–carbon nanocomposites have been manufactured under IR heating. The size of FeCo nanoparticles have been found to be tailored by varying synthesis temperature and metal concentration. The saturation magnetization has been shown to increase as the synthesis temperature or metal concentration rises, with an attendant decrease in coercive force. The electromagnetic properties of FeCo/C nanocomposites have been studied. Complex magnetic permittivity measurements have shown that variation of the synthesis temperature or metal concentration can appreciably increase magnetic loss, which leads to a shift of the band of minimum electromagnetic reflectivity in the frequency range 3–12 GHz.     

Triton X-100六角液晶相中制备镁铝层状双金属氢氧化物纳米片及其药物载体应用

以Triton X-100 六角相溶致液晶作微反应器, 采用共沉淀法制备了镁铝层状双金属氢氧化物(LDHs)纳米薄片(L-LDHs). 以双氯芬酸钠(DS)为药物模型分子, 采用离子交换法制备了DS插层LDHs (DS/L-LDHs)纳米杂化物, 在37.0 ℃、pH=7.2的缓冲溶液中, 考察了纳米杂化物的药物释放性能, 并与传统溶液共沉淀法制备的镁铝LDHs (S-LDHs)纳米片状颗粒进行了对比. 采用粉末X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱、场发射扫描电镜(FE-SEM)、透射电镜(TEM)和N₂吸附-脱附等技术对所制备的LDHs和DS/LDHs 样品的晶体结构、比表面积、形貌特征等进行了表征. 结果表明, L-LDHs比S-LDHs具有更低的片厚度, 更高的比表面积和药物负载量, 所形成的DS/L-LDHs纳米杂化物药物释放速率也明显低于DS/S-LSHs, 即L-LDHs更适于作药物载体. DS/L-LDHs纳米杂化物的药物释放过程符合准二级动力学方程, 受颗粒内部扩散过程控制. 溶致液晶模板法可实现LDHs的形貌可控制备, 为LDHs基功能材料的研发提供了新途径.     

pH sensitive swelling and releasing behavior of nano-gels based on polyaspartamide graft copolymers

Dendritic and porous Ag-Pd alloy nanostructures were successfully fabricated on the surface of silicon substrate using the co-reduction method and galvanic replacement reaction, respectively. The molar compositions of Ag and Pd in the alloy could be modulated by controlling the molar ratios of metal precursors and reaction time. The Ag-Pd alloy nanostructures were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX), and X-ray diffraction (XRD). The morphology and phase of Au-Pd alloy nanostructures were discussed as a function of molar ratios of metal precursors and reaction time. In addition, the morphology and composition-dependent surface-enhanced Raman scattering (SERS) of the as-synthesized Ag-Pd alloy nanostructures were investigated. The SERS enhancement factor was estimated and SERS mapping was performed to prove the homogeneity of these substrates. The results indicate that as-synthesized dendritic and porous Ag-Pd alloy nanostructures are good candidates for SERS spectroscopy.     

Covalent assembly of metal nanoparticles on cellulose fabric and its antimicrobial activity

We develop an antimicrobial active robust metal-cellulose nanohybrid by covalent assembly of metal nanoparticles on cellulose fabric using a simple impregnation of thiol-modified cellulose fabric in colloidal silver (Ag) or palladium (Pd) nanoparticle solutions. The combined results of high resolution transmission electron microscopy (HR-TEM), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDXS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) reveal that the nanoparticles are highly loaded and dispersed in the thiol-modified cellulose fabric, and X-ray photoelectron spectroscopy (XPS) analysis reveals that the nanoparticles are immobilized in the fabric by a strong and stable covalent bond with thiol functional group. This robust covalent linkage between the nanoparticles and the fabric leads to a remarkable suppression of the release of metal nanoparticles from the fabric. In addition, the metal-cellulose nanohybrids show high antimicrobial activity in excess of 99.9 % growth inhibition of the microorganism. Thus, we anticipate that our metal-cellulose nanohybrid may not only protect cell damage caused by penetration and fixation of metal nanoparticles into the human body but also act as a sustainable biomedical textile.     

Thermal analysis,crystal structure and magnetic properties of Cr-doped Ni–Mn–Sn high-temperature magnetic shape memory alloys

The superiority of NiMnSn alloy on NiMnGa alloy is far ahead in term of some physical characteristics, and therefore, the development of this alloy group is very important. In this work, Ni₅₀Mn_45−xSn₅Cr_x magnetic shape memory alloys were produced for x = 0, 4, 6, 10 and 12. Thermal analysis was performed on produced alloys in a wide range (200–1000 °C) by using differential scanning calorimetry, thermogravimetric and differential thermal analysis. According to the thermal analysis results, the austenite ↔ martensite transformation temperatures of the NiMnSn alloy decreased with increasing chromium content. Furthermore, the increase in the chromium ratio caused single-phase transformation due to the multiple phase transformation that was observed in the NiMnSn alloy. In addition, the crystal structure and microstructure analyses of the alloys were determined by using X-ray diffraction and scanning electron microscopy–energy-dispersive X-ray spectroscopy. In all cases, martensite and gamma phase were encountered and the gamma phase ratio was found to be increased by chromium addition. The magnetization characteristics were studied by using physical properties measurement systems device, and it was found that the alloys have a considerably small response to magnetic flux.

     

磁场和稀土Ce介入下化学镀Co-Ni-B合金的晶化行为

化学镀钴-镍-硼;晶体结构;稀土重金属;磁场和稀土Ce介入下化学镀Co-Ni-B合金的晶化行为     

功函数测量研究氧与银和银-钯合金表面的相互作用

在超高真空条件下, 采用电子束阻挡势技术测量固体表面功函数连续变化, 并与AES, TDS等手段相配合, 研究了氧在Ag和Ag-Pd合金表面的吸附和脱附动力学。结果表明, 在Ag和Ag-Pd合金表面的两种不同的氧吸附态, 具有相反的电荷转移效应, 未解离的分子态吸附降低了表面功函数, 而解离的原子态氧吸附使表面功函数明显升高。与纯银相比, 氧在银钯合金表面吸附具有较小的粘附系数和较大的偶极矩。银钯合金组成变化时功函数和AES的连续测量表明, 表面结构从无序向有序转变和表面银偏析均为功函数降低过程。     

Concise,Single-Step Synthesis of Sulfur-Enriched Graphene: Immobilization of Molecular Clusters and Battery Applications

The concise synthesis of sulfur-enriched graphene for battery applications is reported. The direct treatment of graphene oxide (GO) with the commercially available Lawesson's reagent produced sulfur-enriched-reduced GO (S-rGO). Various techniques, such as X-ray photoelectron spectroscopy (XPS), confirmed the occurrence of both sulfur functionalization and GO reduction. Also fabricated was a nanohybrid material by using S-rGO with polyoxometalate (POM) as a cathode-active material for a rechargeable battery. Transmission electron microscopy (TEM) revealed that POM clusters were individually immobilized on the S-rGO surface. This battery, based on a POM/S-rGO complex, exhibited greater cycling stability for the charge-discharge process than a battery with nanohybrid materials positioned between the POM and nonenriched rGO. These results demonstrate that the use of sulfur-containing groups on a graphene surface can be extended to applications such as the catalysis of electrochemical reactions and electrodes in other battery systems.     

Co-Ni合金薄膜的电化学外延及同步辐射XMCD研究

采用电化学循环伏安法在单晶GaAs(001)衬底上外延沉积了Co-Ni二元合金薄膜. 扫描电子显微镜观察结果显示, 薄膜厚度约180 nm, 其表面由约40 nm大小的颗粒组成. 用X射线荧光法确定了薄膜的组分为Co66Ni34, XRD确定了其为面心立方结构. 用同步辐射圆偏振软X射线分别测量了样品中Co和Ni的吸收谱(XAS), 从而得到X射线磁性圆二色(XMCD)谱, 通过加和定则分别计算出了合金中Co和Ni的轨道磁矩和自旋磁矩, 与纯的Co和Ni样品相比, 它们都有不同程度的增加.