A general method for the synthesis of nanostructured large-surface-area materials through the self-assembly of functionalized nanoparticles

A general synthetic method for the preparation of nanostructured materials with large surface area was developed by using nanoparticle building blocks. The preparation route involves the self-assembly of functionalized nanoparticles in a liquid-crystal phase. These nanoparticles are functionalized by using difunctional amino acid species to provide suitable interactions with the template. Optimum interactions for self-assembly of the nanoparticles in the liquid-crystal phase were achieved with one -NH2 group anchored to the nanoparticle surface per 25 A(2). To maximize the surface area of these materials, the wall thicknesses are adjusted so that they are composed of a monolayer of nanoparticles. To form such materials, numerous parameters have to be controlled such as the relative volume fraction of the nanoparticles and the template and size matching between the hydrophilic component of the copolymer and nanoparticles. The surface functionalization renders our synthetic route independent of the nanoparticles and allows us to prepare a variety of nanostructured composite materials that consist of a juxtaposition of different discrete oxide nanoparticles. Examples of such materials include CeO2, ZrO2, and CeO2-Al(OH)3 composites.     

Both core- and shell-cross-linked nanogels: photoinduced size change, intraparticle LCST, and interparticle UCST thermal behaviors

New thermal- and photoresponsive core-shell nanogel particles were obtained from self-assembly in aqueous solution of a double-hydrophilic block copolymer (DHBCP) of which the two blocks could be photo-cross-linked via the reversible photodimerization and photocleavage of coumarin moieties. The diblock copolymer, consisting of poly[N,N-dimethylacrylamide-co-4-methyl-[7-(methacryloyl)oxyethyloxy]coumarin] and poly[N-isopropylacrylamide-co-4-methyl-[7-(methacryloyl)oxyethyloxy]coumarin] (P(DMA-co-CMA)-b-P(NIPAM-co-CMA)), was synthesized by using reversible addition-fragmentation chain transfer (RAFT) polymerization. At T > LCST of the P(NIPAM-co-CMA) block, core-shell micelles were formed and UV light irradiation at λ > 310 nm resulted in cross-linking of both the micelle core of P(NIPAM-co-CMA) and the micelle shell of P(DMA-co-CMA); subsequent cooling of the solution to T < LCST gave rise to water-soluble, swollen nanogel particles. Upon UV light irradiation at λ < 260 nm, the decrease of cross-linking density could increase the swelling of nanogel particles by ～23% in diameter. By alternating irradiation with the different wavelengths, the average hydrodynamic diameter of nanogel particles was tunable between ～58 and ～47 nm. Interestingly, upon further cooling of the solution, aggregation occurred for nanogel particles with a moderate cross-linking density (10%-40% dimerization of coumarin moieties). Therefore, such core- and shell-cross-linked nanogel could display both "intraparticle" LCST (solubility of polymer chains forming the core) and "interparticle" UCST (solubility of particles). The possible mechanism and the effect of dimerization degree on the UCST behavior were discussed.     

磁性Fe_3O_4-聚吡咯纳米微球的合成与表征

报道了具有核壳结构的Fe3O4 聚吡咯磁性纳米微球的合成方法和表征结果 .微球同时具有导电性和磁性能 .在优化的实验条件下 ,可得到饱和磁化强度为 2 3 4emu g ,矫顽力为 45 2Oe的磁性微球 .微球的导电性随着微球中Fe3O4含量的增加而下降 .微球的磁性能则随着Fe3O4含量的增加而增大 .Fe3O4磁流体的粒径和磁性聚吡咯微球的粒径均在纳米量级 .纳米Fe3O4粒子能够提高复合物的热性能 .实验表明 ,磁流体和聚吡咯之间存在着一定的相互作用 ,正是这种相互作用使磁性聚吡咯纳米微球的热稳定性提高 .     

Enhanced Wettability Changes by Synergistic Effect of Micro/Nanoimprinted Substrates and Grafted Thermoresponsive Polymer Brushes

Thermoresponsive polymer brushes are grafted on micro/nanostructured polymer substrates as new intelligent interfaces that synergistically enhance wettability changes in response to external temperature stimuli. Thermoplastic poly(styrene‐co‐4‐vinylbenzyl chloride) [P(St‐co‐VBC)] is synthesized using radical polymerization and spin‐coated on a glass substrate. Micro/nanopillar and hole patterns are imprinted on the P(St‐co‐VBC) layer using thermal nanoimprint lithography. Poly(N‐isopropylacrylamide) (PIPAAm) brushes are grafted on the micro/nanostructured P(St‐co‐VBC) layer through surface‐initiated atom‐transfer radical polymerization using 4‐vinylbenzyl chloride as the initiator. The imprinted micro/nanostructures and grafted PIPAAm brush chain lengths affect the surface wettability. Combinations of nanopillars or nanoholes (diameter 500 nm) and longer PIPAAm brushes enhance hydrophobic/hydrophilic changes in response to temperature changes, compared with the flat substrate. The thermoresponsive hydrophobic/hydrophilic transition is synergistically enhanced by the nanostructured surface changing from Cassie–Baxter to Wenzel states. This PIPAAm‐brush‐modified micro/nanostructured P(St‐co‐VBC) is a new intelligent interface that effectively changes wettability in response to external temperature changes.

     

Hierarchical structured Ni nanoring and hollow sphere arrays by morphology inheritance based on ordered through-pore template and electrodeposition

Fabrication of micro/nano-hierarchical Ni ordered nanostructured arrays is demonstrated by electrochemical deposition on the ordered alumina through-pore template induced by solution-dipping the colloidal monolayer. The morphology of the Ni nanostructured arrays exhibits a ringlike or hollow spherical structure depending on the template geometry and appropriate deposition parameters. The skeletons of the arrays are of floc- or flakelet-like fine structure on the nanoscale. The formation of such morphologies is attributed to the preferential growth along the inner wall of the alumina pores, while the nanoflakelet fine structure originates from a morphology inheritance process or the transitional product Ni(OH)2 which leads to the final nanostructured Ni crystals. This morphology inherence could be useful in the field of nanofabrication. Such micro/nano-hierarchically structured arrays show good magnetic properties and will find applications in the fields of catalysis, magnetics, optoelectrics, surface-enhanced Raman scattering (SERS), and new nanodevices.     

Electromagnetic functionalized cage-like polyaniline composite nanostructures

Novel cage-like and electromagnetic functional polyaniline (PANI)/CoFe2O4 composite nanostructures, in which the self-assembled PANI nanofibers (approximately 15 nm in diameter) entwined around the octahedral CoFe2O4 magnet acting as the nucleation site or template, were successfully prepared by FeCl3 as either oxidant and dopant via a self-assembly process. The coordination effect of the magnet as a nucleation site or template and the magnetic interaction between the PANI nanofibers and CoFe2O4 as a driving force results in such cage-like nanostructures. The cage-like composite nanostructures not only have high conductivity (sigmamax approximately 5.2 S/cm), but also show a typical ferromagnetic behavior.     

Fabrication of hybrid nanostructured arrays using a PDMS/PDMS replication process

In the study, a novel and low cost nanofabrication process is proposed for producing hybrid polydimethylsiloxane (PDMS) nanostructured arrays. The proposed process involves monolayer self-assembly of polystyrene (PS) spheres, PDMS nanoreplication, thin film coating, and PDMS to PDMS (PDMS/PDMS) replication. A self-assembled monolayer of PS spheres is used as the first template. Second, a PDMS template is achieved by replica moulding. Third, the PDMS template is coated with a platinum or gold layer. Finally, a PDMS nanostructured array is developed by casting PDMS slurry on top of the coated PDMS. The cured PDMS is peeled off and used as a replica surface. In this study, the influences of the coating on the PDMS topography, contact angle of the PDMS slurry and the peeling off ability are discussed in detail. From experimental evaluation, a thickness of at least 20 nm gold layer or 40 nm platinum layer on the surface of the PDMS template improves the contact angle and eases peeling off. The coated PDMS surface is successfully used as a template to achieve the replica with a uniform array via PDMS/PDMS replication process. Both the PDMS template and the replica are free of defects and also undistorted after demoulding with a highly ordered hexagonal arrangement. In addition, the geometry of the nanostructured PDMS can be controlled by changing the thickness of the deposited layer. The simplicity and the controllability of the process show great promise as a robust nanoreplication method for functional applications.     

聚合物加工中微纳导电网络构筑及其传感器应用研究进展

设计和构筑有序微纳结构导电网络是聚合物基导电复合材料(CPC)加工中的关键问题,对于降低复合材料的逾渗阈值,提高其电导率和电阻响应灵敏性具有重要意义。本文综述了近年来CPC材料加工中利用双逾渗网络构筑法、隔离结构构筑法、气凝胶模板法、乳液模板法、3D打印法在聚合物基体中构建微纳导电网络及其在柔性传感器中的应用研究进展,并对未来CPC材料及其柔性传感器制备的加工新方法进行了展望。     

Magnetic properties of monodispersed Ni/NiO core-shell nanoparticles

We have recently developed a method to fabricate monodispersed Ni/NiO core-shell nanoparticles by pulsed laser ablation. In this report, the size-dependent magnetic properties of monodispersed Ni/NiO core-shell nanoparticles were investigated. These nanoparticles were formed in two steps. The first was to fabricate a series of monodispersed Ni nanoparticles of 5 to 20 nm in diameter using a combination of laser ablation and size classification by a low-pressure differential mobility analyzer (DMA). The second step was to oxidize the surfaces of the Ni particles in situ to form core-shell structures. A superconducting quantum interference device (SQUID) magnetometer was used to measure the magnetic properties of nanostructured films prepared by depositing the nanoparticles at room temperature. Ferromagnetism was observed in the magnetic hysteresis loop of the nanostructured films composed of core-shell nanoparticles with core diameters smaller than the superparamagnetic limit, which suggests the spin of Ni core was weakly exchange coupled with antiferromagnetic NiO shell. In contrast, smaller nanoparticles with core diameters of 3.0 nm exhibited superparamagnetism. The drastic change in the hysteresis loops between field-deposited and zero-field-deposited samples was attributable to the strong anisotropy that developed during the magnetic-field-assisted nanostructuring process.     

氯醇盐溶胶-凝胶法纳米结构氧化钨薄膜的光谱学特性

由非离子型Gemini表面活性剂TMDD(HO(EO)xC14(EO)yOH)为结构导向模板, 改进EISA(挥发诱导自组装)镀膜工艺经300 ℃焙烧制得具有连续、均一和光学透明特点的蠕虫介孔纳米晶孔壁氧化钨薄膜. 采用SEM、TEM和Raman光谱对此种薄膜的介孔纳米结构进行了表征, 通过光谱电化学、XPS和椭偏谱等方法, 研究了该薄膜在电解质溶液中的电致变色行为. 结果表明, 所制备的纳米结构氧化钨薄膜在633 nm波长处的循环可逆透过率调制幅度可达75%以上, 并且其电致变色机理具有显著的双注入吸收调制特性.     

Effects of oligoDNA template length and sequence on binary self-assembly of a nucleotide bolaamphiphile

Templated self-assembly of nucleotide bolaamphiphile 1 (in which a 3'-phosphorylated thymidine moiety is connected to each end of a long oligomethylene chain) with a 10-, 20-, 30-, or 40-meric single-stranded oligoadenylic acid (2, 3, 4, or 5) led to the formation of right-handed helical nanofibers in 0.1x Tris/EDTA (TE) buffer solutions. The helical pitch increased as the length of the oligoadenylic acid template increased. DNA composed of oligoadenylic and oligocytidylic acid sequences (6, 7, and 8) also acted as templates to induce the formation of helical nanofiber structures. The diameter of the nanofibers remained constant (6-6.6 nm) irrespective of the template used. The binary self-assembly of 1 with 4 also produced higher-order, double-stranded nanofibers.     

A "non-sticky" superhydrophobic surface prepared by self-assembly of fluoroalkyl phosphonic acid on a hierarchically micro/nanostructured alumina gel film

A hierarchically micro/nanostructured alumina gel film was prepared by using a simple sol-gel process; upon self-assembly of fluoroalkyl phosphonic acid, a "non-sticky" superhydrophobic surface was obtained.     

Surface-guided self-assembly of silver nanoparticles on edges of heterogeneous surfaces

A general method for the generation of two-dimensional (2D) ordered silver nanoparticles (av 45 nm) ring array has been demonstrated via controllable self-assembly. The selective self-assembly is conducted on the edges of a gold coated polyelectrolyte film. This film is fabricated using the monolayer polystyrene (PS) spheres (av 600 nm) on a substrate as template, followed by depositing a positively charged polyelectrolyte and gold colloids (av 17 nm) via the layer-by-layer (LbL) self-assembly technique, and finally by eliminating the PS monolayer. This gold coated polyelectrolyte film has a regular pattern of sharp edges, and those edges are composed of abundant polyelectrolyte. This heterogeneous surface is easily prepared and universal for site-selective absorption of nanoparticles (silver nanoparticles in this paper, av 45 nm). This surface-guided self-assembly is powerful for fabricating micro/nanostructures on the edges of prepatterns. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the products.     

Solution self-assembly of magnetic light modulators from exfoliated perovskite and magnetite nanoparticles

Covalent linkage of oleic acid ligated Fe3O4 spheres (9 nm) with sheetlike [H1-xCa2Nb3O10] particles (300 x 300 x 2 nm) yields, depending on conditions, submicro- or microscale stacks, which on their surfaces are decorated with magnetite nanoparticles. Due to the optical anisotropy of the sheetlike Ca2Nb3O10 building blocks and due to the superparamagnetic nature of the Fe3O4 components, the nanostructured composites exhibit magnetically controllable birefringence and light-scattering properties in solution.     

聚吡咯/Ba_(0.9)Nd_(0.1)Fe_(11.5)Cr_(0.5)O_(19)复合物的可控合成及电磁性能

用溶胶凝胶法制备了一系列Nd掺杂Ba-铁氧体粉末(Ba1-xNdxFe11.5Cr0.5O19,x=0.00,0.05,0.10,0.15,0.20),选取磁性能相对较好的Ba0.9Nd0.1Fe11.5Cr0.5O19作为磁核,通过原位聚合法制备了不同铁氧体含量的聚吡咯/Ba0.9Nd0.1Fe11.5Cr0.5O19(PPy/BNFCO)复合物.用X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、红外光谱(FTIR)、振动样品磁强计(VSM)、四探针测试仪和矢量网络分析仪等表征了铁氧体粉末和复合物微粒的结构、形貌以及电磁性能.结果表明,Nd的掺杂明显改变了Ba-铁氧体的饱和磁化强度和矫顽力;PPy/BNFCO复合物具有比较明显的核壳结构;复合物的饱和磁化强度随BNFCO含量的增加而增大;电导率则与PPy含量成正比,mpy/mBNFCO=5/1为复合体系渗流阈值;复合物对电磁波的反射损耗和有效带宽是PPy和ZCGFO协同作用的结果,当mpy/mBNFCO为5/1时,PPy/ZCGFO复合物中组分间的协同作用达到最大,其反射峰值和有效带宽分别达到-27.68dB和9.04GHz.PPy/ZCGFO复合物由于良好的微波吸收性能,有望成为电磁波吸收与屏蔽领域的候选材料.     

磁性聚苯胺纳米微球的合成与表征

报道了具有核壳结构的Fe3O4-聚苯胺磁性纳米微球的合成方法和表征结果.微球同时具有导电性和磁性能.在优化的实验条件下,可得到饱和磁化强度Ms为55.4 emu/g,矫顽力Hc为62 Oe的磁性微球.微球的导电性随着微球中Fe含量的增加而下降.微球的磁性能则随着Fe含量的增加而增大.Fe3O4磁流体的粒径和磁性聚苯胺微球的粒径均在纳米量级.纳米Fe3O4粒子能够提高复合物的热性能.实验表明,磁流体和聚苯胺之间可能存在着一定的相互作用,但这种相互作用较为复杂,难于研究     

Selective recognition of sesamol using molecularly imprinted polymers containing magnetic wollastonite

The magnetic molecularly imprinted polymers (MMIPs) have been synthesized using piperonal molecules as dummy template and magnetic wollastonite composites as support. The resulting composites were applied to selective recognition of sesamol from aqueous solution. MMIPs were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) analysis, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). MMIPs were demonstrated with an imprinted polymer film (90-100 nm) and exhibited magnetic property (M(s) =8.60 emu/g) and thermal stability. The effective average diameter of the Fe(3) O(4) nanoparticles was about 10 nm and the thickness of magnetic film was about 160 nm. Batch mode adsorption studies were carried out to investigate the specific adsorption equilibrium, kinetics and selective recognition. The Langmuir isotherm model was fitted to the equilibrium data better than the Freundlich model, and the kinetic properties were well described by the pseudo-second-order equation. The value of E(a) in this study was 5.35 kJ/mol for MMIPs. In addition, the selective recognition experiments demonstrated that MMIPs have specific recognition ability toward sesamol.     

Thermodynamic properties of the unique self-assembly of {Mo72Fe30} inorganic macro-ions in salt-free and salt-containing aqueous solutions

Static and dynamic laser light scattering techniques are used to monitor the slow self-assembly of 2.5-nm-diameter, hollow spherical, fully hydrophilic heteropolyoxometalate {Mo72Fe30} macro-ions into single-layer vesicle-like "blackberries" (averaging approximately 50-60 nm in diameter) in dilute salt-free and salt-containing aqueous solutions, to obtain the thermodynamic properties of the unique self-assembly. A very high activation energy is observed during the transition from the single ion (general solute state) to blackberries (so-called "second solute state"), which might be responsible for the interestingly slow self-assembly process in dilute solutions. The thermodynamic parameters of the blackberry formation can be affected by adding simple electrolytes into the solution, because the electrostatic interactions are responsible for the unique self-assembly, and the effects of various anions and cations (in the low salt concentration regimes) are discussed. Multivalent anions make the single {Mo72Fe30} macro-ions more stable and make the blackberry formation more difficult. Small cations carrying more charges tend to accelerate the self-assembly process. This is the first study on the thermodynamic properties of the novel self-assembly in dilute solutions and the equilibrium and transition between the two solute states of macro-ions in solution.     

胶体刻蚀——纳米结构化表面的构筑与应用

综述了近年来胶体刻蚀领域的研究进展, 分别讨论了基于胶体微粒和胶体晶体为模板的可控沉积与可控刻蚀及在固体平面基质、曲面基质和气液界面等不同基质上构筑结构化表面的方法. 同时还探讨了利用胶体刻蚀方法形成的微纳结构在光、电、磁以及表面润湿和生物学等方面的应用.     

Addition and redox reactivity of hydrogen sulfides (H2S/HS⁻) with nitroprusside: new chemistry of nitrososulfide ligands

The nitroprusside ion [Fe(CN)(5)NO](2-) (NP) reacts with excess HS(-) in the pH range 8.5-12.5, in anaerobic medium ("Gmelin" reaction). The progress of the addition process of HS(-) into the bound NO(+) ligand was monitored by stopped-flow UV/Vis/EPR and FTIR spectroscopy, mass spectrometry, and chemical analysis. Theoretical calculations were employed for the characterization of the initial adducts and reaction intermediates. The shapes of the absorbance-time curves at 535-575 nm depend on the pH and concentration ratio of the reactants, R=[HS(-)]/[NP]. The initial adduct [Fe(CN)(5)N(O)SH](3-) (AH, λ(max) ≈570 nm) forms in the course of a reversible process, with k(ad)=190±20 M(-1)s(-1) , k(-ad)=0.3±0.05 s(-1) . Deprotonation of AH (pK(a)=10.5±0.1, at 25.0 °C, I=1 M), leads to [Fe(CN)(5)N(O)S](4-) (A, λ(max)=535 nm, ε=6000±300 M(-1) cm(-1) ). [Fe(CN)(5)NO](.)(3-) and HS(2)(.)(2-) radicals form through the spontaneous decomposition of AH and A. The minor formation of the [Fe(CN)(5)NO](3-) ion equilibrates with [Fe(CN)(4)NO](2-) through cyanide labilization, and generates the "g=2.03" iron-dinitrosyl, [Fe(NO)(2)(SH)(2)](-) , which is labile toward NO release. Alternative nucleophilic attack of HS(-) on AH and A generates the reactive intermediates [Fe(CN)(5)N(OH)(SH)(2)](3-) and [Fe(CN)(5)N(OH)(S)(SH)](4-) , respectively, which decompose through multielectronic nitrosyl reductions, leading to NH(3) and hydrogen disulfide, HS(2)(-) . N(2)O is also produced at pH≥11. Biological relevance relates to the role of NO, NO(-) , and other bound intermediates, eventually able to be released to the medium and rapidly trapped by substrates. Structure and reactivity comparisons of the new nitrososulfide ligands with free and bound nitrosothiolates are provided.