Nanomodification of living organisms by biomimetic mineralization

In nature, a few living organisms such as diatoms, magnetotactic bacteria, and eggs have developed specific mineral structures, which can provide extensive protection or unique functions. However, most organisms do not have such structured materials due to their lack of biomineralization ability. The artificial introduction of biomimetic-constructed nanominerals is challenging but holds great promise. In this overview, we highlight two typical types of mineral-living complex systems. One involves biological surface-induced nanomaterials, which produces artificial living-mineral core-shell structures such as the mineralencapsulated yeast, cyanobacteria, bacteria and viruses. The other involves internal nanominerals that could endow organisms with unique structures and properties. The applications of these biomimetic generated nanominerals are further discussed, mainly in four potential areas: storage, protection, “stealth” and delivery. Since biomineralization combines chemical, nano and biological technologies, we suggest that nanobiomimetic mineralization may open up another window for interdisciplinary research. Specifically, this is a novel material-based biological regulation strategy and the integration of living organisms with functional nanomaterials can create “super” or intelligent nanoscale living complexes for biotechnological practices.      

木垛型壳聚糖多孔支架的磷酸化改性和仿生矿化

为提高壳聚糖支架材料的孔隙率及矿化程度,通过磷酸化表面改性和仿生矿化制备了磷酸化(PCSW)和生物矿化(BMCW)木垛型壳聚糖多孔支架.FTIR结果显示,壳聚糖分子中有磷酸根的引入.XRD结果表明,矿化24 h后支架上形成结晶度较高的磷酸钙盐晶体,矿化48 h后结晶度明显增加并形成单纯的羟基磷灰石(HA)结晶.SEM观察发现,在支架的内外表面均致密地沉积了HA晶体层.压缩强度测试结果表明,复合支架BMCW矿化48 h的压缩强度为(0.54±0.005) MPa,压缩模量为(5.47±0.65) MPa,BMCW可用作非承重骨组织修复材料.     

木垛型壳聚糖多孔支架的磷酸化改性和仿生矿化

为提高壳聚糖支架材料的孔隙率及矿化程度, 通过磷酸化表面改性和仿生矿化制备了磷酸化(PCSW)和生物矿化(BMCW)木垛型壳聚糖多孔支架。FTIR结果显示, 壳聚糖分子中有磷酸根的引入。XRD结果表明, 矿化24 h后支架上形成结晶度较高的磷酸钙盐晶体, 矿化48 h后结晶度明显增加并形成单纯的羟基磷灰石(HA)结晶。SEM观察发现, 在支架的内外表面均致密地沉积了HA晶体层。压缩强度测试结果表明, 复合支架BMCW矿化48 h的压缩强度为(0.54±0.005) MPa, 压缩模量为(5.47±0.65) MPa, BMCW可用作非承重骨组织修复材料。     

Synthesis and layer-by-layer self-assembly of silver nanoparticles capped by mercaptosulfonic acid

Spherical silver nanoparticles capped by mercaptosulfonic acid with a diameter of about 8 nm were prepared by a simple chemical reaction. The resulting silver nanoparticles were characterized by UV–vis spectroscopy (UV–vis) and transmission electron microscopy (TEM). Using layer-by-layer (LBL) self-assembly technique, the multilayer films containing silver nanoparticles and polycation poly(dialyldimethylammonium chloride) (PDDA) were successfully fabricated. The fabrication process was monitored by UV–vis spectra and the morphology of the multilayer films was investigated by atomic force microscopy (AFM). The cyclic voltammogram (CV) measurements further confirmed that the silver nanoparticles had assembled into the multilayer films successfully. Surface-enhanced Raman spectroscopy (SERS) measurements showed that the multilayer films containing silver nanoparticles could serve as SERS-active substrate.     

Polymer magnetic microactuators fabricated with hot embossing and layer-by-layer nano self-assembly

Polymer-based magnetic microactuators have been fabricated with hot embossing technique and layer-by-layer (LbL) nano self-assembly. Silicon molds are fabricated with conventional UV lithography and wet etching techniques. Hot embossing is used to transfer the patterns from silicon molds to polymethylmethacrylate (PMMA) sheets. The overall processing time for the pattern transfer is less than 20 min. Low-cost devices with massive and rapid replication can be fabricated. Six layers of magnetic iron oxide (Fe2O3) nanoparticles are LbL self-assembled on the PMMA surface as the magnetically sensitive material. Positive photoresist PR1813 is used as the sacrificial layer to protect the gold electrode on the back side of the membrane. LbL nano self-assembly technique provides a simple method to obtain the magnetic film with low cost, short processing time, simple fabrication steps at room temperature. The volume of the magnetic material can be precisely controlled by the number of nano-assembled iron oxide layers. The mechanical, electrical, and magnetic properties of the microactuator are characterized by a laser interferometer. The natural frequency of the actuator is approximately 151 Hz; and the maximum deflection amplitude is about 34 nm. At all frequencies, the increase of the magnetic field increases the deflection amplitude which is in agreement with the theoretical equation.     

基于真空辅助层层自组装的透明柔性纳米芳纶薄膜的制备

通过二甲基亚砜（DMSO）-KOH体系溶解宏观芳纶纤维（AF）成功制备了直径为40~50 nm、长度为2~5 μm的纳米芳纶纤维（NAF）,并利用SEM、TEM、FTIR、Raman和XRD对NAF和AF的微观形貌、化学结构、结晶结构进行了分析。结果表明,NAF与AF具有相似的化学结构,同时NAF保留了AF大部分的结晶结构,只是纤维尺寸有一定的差异。通过真空辅助层层自组装法制备了具有层状致密结构的NAF复合薄膜,该薄膜展现出很好的透明、柔性、耐温性和力学性能,具有一定的亲液性能（接触角为81.5°）及优异的抗液体渗透和抗液体吸收性能。      

Monitoring the layer-by-layer self-assembly of graphene and graphene oxide by spectroscopic ellipsometry

Thin films of graphene oxide, graphene and copper (II) phthalocyanine dye have been successfully fabricated by electrostatic layer-by-layer (LbL) assembly approach. We present the first variable angle spectroscopic ellipsometry (VASE) investigation on these graphene-dye hybrid thin films. The thickness evaluation suggested that our LbL assembly process produces highly uniform and reproducible thin films. We demonstrate that the refractive indices of the graphene-dye thin films undergo dramatic variation in the range close to the absorption of the dyes. This investigation provides new insight to the optical properties of graphene containing thin films and shall help to establish an appropriate optical model for graphene-based hybrid materials.     

层层自组装PDADMAC/PSS纳滤膜的制备

以荷负电的聚砜超滤膜为基膜,采用静态层层自组装技术,制备了PDADMAC/PSS多层聚电解质纳滤膜.考察了支撑盐的种类、浓度、自组装层数对膜的分离性能、荷电性能、亲水性等的影响.研究结果表明,以NaCl为支撑电解质制得的膜具有较高的性能,聚合电解质溶液中支撑电解质的浓度以0.5mol/L为宜;在较优的条件下所制备的(PDADMAC/PSS)5对2g/L Na2SO4的截留率可达93%,通量在1.0MPa下接近60L/(m2.h),对NaCl的截留率仅为9%～13%,通量可达80L/(m2.h).膜表面的荷电量和接触角的变化均反映了聚电解质的交替自组装.以PSS为最外层的膜表面具有很好的负电性和很低的接触角.随着双层数的增加,膜表面的负电荷量的绝对值先逐渐增大,达到一个极大值后又逐渐减少,说明层数并非越多越好;以PSS作为最外层的膜具有很好的亲水性.     

交替沉积自组装法制备聚苯胺复合薄膜的研究

采用交替沉积自组装法制备了聚苯胺复合薄膜,用紫外-可见光谱、傅立叶红外光谱、热重法、循环伏安法对薄膜的结构、性能进行了表征和分析.     

聚苯胺/磺化酞菁铜自组装复合薄膜的制备与表征

运用层层自组装的技术制备了聚苯胺/磺化酞菁铜(PANI/CuTsPc)超分子复合薄膜,并通过紫外-可见-近红外吸收光谱、傅立叶红外光谱、X射线衍射仪与原子力显微镜对薄膜进行了表征与分析.紫外-可见-近红外吸收光谱表明,PANI和CuTsPe具有良好的层层自组装特性,沉积过程具有均匀性与重复性;傅立叶红外光谱表明,复合薄膜是由PANI和CuTsPc组成的,PANI和cuTsPc通过静电力的作用组装成膜;X射线衍射结果表明,复合薄膜是非晶态的;原子力显微镜观察到薄膜表面是比较均匀和致密的,但有一定的粗糙度.     

层层自组装法制备光敏变色复合薄膜及其性能表征

采用层层自组装法成功制备了以光敏变色材料和聚乙烯醇(PVA)为基质的光敏变色复合薄膜。采用傅里叶变换红外光谱(FT-IR)和扫描电镜(SEM)分别表征了光敏变色复合薄膜的化学组成和横断面形貌;研究了复合薄膜在紫外光照射下的光敏变色性能;用万能力学试验机和热重分析(TGA)分别检测了复合薄膜的力学性能和热稳定性能。结果表明:光敏变色材料与聚乙烯醇通过氢键结合形成光敏变色复合薄膜;SEM分析表明,光敏变色复合薄膜是典型的"三明治"结构;随着光敏变色材料浓度的增加,复合薄膜在紫外光照射下的总色度指数(ΔE*)呈现递增趋势;光敏变色复合薄膜的拉伸强度随光敏变色材料浓度的增加先增加后降低;复合薄膜的断裂伸长率随光敏变色材料的增加逐渐降低;TGA分析表明,光敏变色复合薄膜的热稳定性介于聚乙烯醇膜与光敏变色物质之间。     

Molecular layer-by-layer self-assembly and mercury sensing characteristics of novel brush polymers bearing thymine moieties

Two new brush polyoxyethylenes bearing thymine moieties at the bristle ends have been synthesized as model polymers in which the chemical loading of the thymine functional group into the polymer is maximized: poly(oxy(11-thyminoacetyloxyundecylthiomethyl)ethylene) (PECH(S)-T) and poly(oxy(11-thyminoacetyloxyundecylsulfonylmethyl)ethylene) (PECH(SO(2))-T). These brush polymers are thermally stable up to around 225 °C, and their glass transitions occur in the range 23-27 °C, but they have significantly different properties despite the similarity of their chemical structures. In particular, PECH(SO(2))-T films exhibit better performance in sensing mercury ions than PECH(S)-T films. These differences were found to originate in the differences between their morphological structures. The PECH(SO(2))-T film has a multi-bilayer structure without interdigitation, in which the layers stack along the out-of-plane of the film and provide a thymine-rich surface. In contrast, the PECH(S)-T film is amorphous with a relatively low population of thymine moieties at the surface. This study demonstrated that a thymine-rich surface is required for recyclable thymine-based polymers to provide highly improved sensitivity and selectivity as well as full reversibility in the sensing of mercury ions. A thymine-rich surface can be achieved with a brush polymer bearing thymine moieties that can self-assemble into a multi-bilayer structure. Because of the thymine-rich surface, the PECH(SO(2))-T thin films even in only 6 nm thickness demonstrate the detection of mercury ions in aqueous solutions with a detection limit of 10(-6) M.     

Fabrication of graphene thin films based on layer-by-layer self-assembly of functionalized graphene nanosheets

In this study, we present a facile means of fabricating graphene thin films via layer-by-layer (LbL) assembly of charged graphene nanosheets (GS) based on electrostatic interactions. To this end, graphite oxide (GO) obtained from graphite powder using Hummers method is chemically reduced to carboxylic acid-functionalized GS and amine-functionalized GS to perform an alternate LbL deposition between oppositely charged GSs. Specifically, for successful preparation of positively charged GS, GOs are treated with an intermediate acyl-chlorination reaction by thionyl chloride and a subsequent amidation reaction in pyridine, whereby a stable GO dispersibility can be maintained within the polar reaction solvent. As a result, without the aid of additional hybridization with charged nanomaterials or polyelectrolytes, the oppositely charged graphene nanosheets can be electrostatically assembled to form graphene thin films in an aqueous environment, while obtaining controllability over film thickness and transparency. Finally, the electrical property of the assembled graphene thin films can be enhanced through a thermal treatment process. Notably, the introduction of chloride functions during the acyl-chlorination reaction provides the p-doping effect for the assembled graphene thin films, yielding a sheet resistance of 1.4 kΩ/sq with a light transmittance of 80% after thermal treatment. Since the proposed method allows for large-scale production as well as elaborate manipulation of the physical properties of the graphene thin films, it can be potentially utilized in various applications, such as transparent electrodes, flexible displays and highly sensitive biosensors.     

Fabrication of nanofiltration membranes via covalent layer-by-layer self-assembly for charged organic pollutants treatment

Journal of Materials Science - Developing a nanofiltration membrane for organic pollutants is regarded as a significant trial. In this work, composite nanofiltration (NF) membranes were reasonably...     

钛表面层层组装胶原与肝素改善血液相容性的研究

为了改进钛表面的血液相容性，本实验通过电荷作用层层组装带正电的细胞外基质胶原和带负电的肝素，在钛表面形成多层仿生膜，以改善钛表面的血液相容性。钛通过氢氧化钠处理，表面形成多孔结构，并产生碱性羟基，之后将其浸泡于多聚赖氨酸溶液中，然后将材料交替浸泡于肝素和胶原中，最后一层为肝素，通过电荷吸引形成多层膜．通过傅立叶红外漫反射（FTTR）检测各步反应后表面基团的变化，通过扫描电子显微镜（SEM）观察表面形貌的变化，初步说明肝素已经结合在材料表面；血小板黏附实验直观反应组装膜有良好的血液相容性。通过本实验说明这种改性方法对于材料血液相容性的改善有一定价值。     

Fabrication of a nanocarrier system through self-assembly of plasma protein and its tumor targeting

Human serum albumin (HSA) nanoparticles hold great promise as a nanocarrier system for targeted drug delivery. The objective of this study was to explore the possibility of preparing size controllable albumin nanoparticles using the disulfide bond breaking reagent β-mercaptoethanol (β-ME). The results showed that the protein concentration and temperature had positive effects on the sizes of the albumin nanoparticles, while pH had a negative effect on the rate of nanoparticle formation. The addition of β-ME induced changes in HSA secondary structure and exposed the hydrophobic core of HSA, leading to the formation of nanoparticles. Human serum albumin nanoparticles could be internalized by MCF-7 cells and mainly accumulated in cytoplasm. After injection in tumor bearing mice, the HSA nanoparticles accumulated in tumor tissues, demonstrating the targeting ability of the nanoparticles. Therefore, human serum albumin can be fabricated into nanoparticles by breaking the disulfide bonds and these nanoparticles exhibit high tumor targeting ability. Human serum albumin nanoparticles could be ideal for the targeted delivery of pharmacologically active substances.     

层状自组装聚苯胺纳米复合电致变色薄膜的制备与性能

质轻、柔性、多色电致变色材料是柔性电致变色显示技术实用化、进而取代目前阴极射线管和液晶显示技术的关键。主链共轭型本征态导电聚合物聚苯胺因其原料来源广泛、转换电势低、变色范围宽、易于制成柔性薄膜而成为制备全固态柔性电致变色器件的首选材料。基于静电作用的层状自组装技术，能在分子层次上实现诸多材料的复合，并实现结构与性能的调控，因此成为设计组装具有特定性能的聚苯胺纳米复合电致变色薄膜的重要方法。讨论了层状自组装聚苯胺纳米复合电致变色薄膜的制备与性能，认为采用结构与性能可控的纳米结构层状自组装技术制备聚苯胺纳米复合电致变色薄膜是提高其综合性能并最终实用化的重要途径。     

The role of nanoscale architecture in supramolecular templating of biomimetic hydroxyapatite mineralization

Understanding and mimicking the hierarchical structure of mineralized tissue is a challenge in the field of biomineralization and is important for the development of scaffolds to guide bone regeneration. Bone is a remarkable tissue with an organic matrix comprised of aligned collagen bundles embedded with nanometer-sized inorganic hydroxyapatite (HAP) crystals that exhibit orientation on the macroscale. Hybrid organic-inorganic structures mimic the composition of mineralized tissue for functional bone scaffolds, but the relationship between morphology of the organic matrix and orientation of mineral is poorly understood. Herein the mineralization of supramolecular peptide amphiphile templates, that are designed to vary in nanoscale morphology by altering the amino acid sequence, is reported. It is found that 1D cylindrical nanostructures direct the growth of oriented HAP crystals, while flatter nanostructures fail to guide the orientation found in biological systems. The geometric constraints associated with the morphology of the nanostructures may effectively control HAP nucleation and growth. Additionally, the mineralization of macroscopically aligned bundles of the nanoscale assemblies to create hierarchically ordered scaffolds is explored. Again, it is found that only aligned gel templates of cylindrical nanostructures lead to hierarchical control over hydroxyapatite orientation across multiple length scales as found in bone.     

Spatial patterning of colloidal nanoparticle-based thin film by a combinative technique of layer-by-layer self-assembly and lithography

A novel approach to generating clear patterns of different types of nanoparticles is presented in this paper. Nanoassembly in the vertical direction was combined with planar micropatterning. This provides industrial applications of a popular layer-by-layer method to produce multilayers of polymers, nanoparticles, and proteins organized on the nanometer scale. A thin film of organic polystyrene spheres was first coated on the pretreated silicon wafer with layer-by-layer self-assembly. Then a layer of aluminium was deposited on the thin film. A layer of positive photoresist was spun on the surface of aluminum and then illuminated with UV light. The exposed parts of the resist were removed and windows were opened above the aluminum. The subsequent etching removed exposed aluminium and left a polystyrene thin film in the open windows. Oxygen plasma was employed to remove the polystyrene thin film on the bottom. Eventually, aluminum and photoresist were removed and only the desired pattern remained. This approach was also employed for the patterning of the silica nanoparticle thin film, a widely used material in various applications. In this case, wet etching was demonstrated to etch silica particles. A scanning electron microscope was used to produce the image of the pattern.     

层层自组装制备PANI/CuTsPc复合薄膜及其性能研究

运用层层自组装技术制备了聚苯胺/磺化酞菁铜(PANI/CuTsPc)超分子复合薄膜,并通过紫外-可见-近红外吸收光谱、红外光谱、电导率测试仪与热分析仪对复合薄膜进行了分析表征以及导电性、光吸收与热稳定性能的研究.紫外-可见-近红外光谱表明,PANI与CuTsPc具有良好的层层自组装特性,沉积过程具有均匀性与重复性,复合薄膜在可见光区和近红外区均具有平而且宽的强吸收谱带;红外光谱表明,PANI和CuTsPc通过静电力的作用成功组装成膜,复合薄膜的共轭体系得到加强;电导率测试结果表明复合薄膜具有较高的电导率,达到了0.3S/cm;热分析结果表明CuTsPc组分的加入使复合薄膜具有良好的热稳定性.