Organic-inorganic nanocomposite materials prepared by the sol-gel route as new ionic conductors in quasi solid state electrolytes

Nanocomposite organic/inorganic materials made through sol-gel method exhibit high values of ionic conductivity when they were impregnated with the redox couple I ₃ ⁻ /I⁻ Two different kinds of nanocomposite materials, depending on the different interactions between silica and poly(ethylene)oxide or poly(propylene)oxide blends, were prepared by the sol-gel technique in room temperature. Gels, for both nanocomposite materials, were obtained by acetic acid catalyzed solvolysis and were regulated by formation of intermediate products, such as silicon ester and -Si-O-Si-oligomers. Time-resolved fluorescence techniques and conductivity measurements were performed in order to define the parameters which allow maximum probe mobility and minimum confinement conditions with the aim to apply these materials in quasi solid state electrolytes. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

有机电致发光白光器件的研究进展

在十多年的时间里,有机电致发光二极管(Organic Lightemitting Diodes,OLEDs)的研究和应用取得了长足的进展。有机电致发光器件具有许多优点,例如:自发光、视角宽、响应快、发光效率高、温度适应性好、生产工艺简单、驱动电压低、能耗低、成本低等,因此有机电致发光器件极有可能成为下一代的平板显示终端。有机电致发光白光器件因为可以用于全彩色显示和照明,已成为OLED研究中的热点。介绍了有机电致发光白光器件的研究进展,按发光的性质将白光器件分为荧光器件和磷光器件两类,按发光层数将白光器件分为单层和多层器件,对相关材料、器件结构、发光机理等方面进行了讨论。     

Hybrid organic–inorganic nanocomposites fabricated with a novel biocompatible precursor using sol-gel processing

The synthesis of hybrid organic–inorganic nanocomposite materials containing biopolymers by the sol-gel processing is often faced with severe difficulties owing to their poor compatibility with the common precursors. The problem was solved when tetrakis(2-hydroxyethyl) orthosilicate (THEOS) was recently suggested for the preparation of sol-gel derived nanocomposites. This article summarizes recent data on novel types of hybrid polysaccharide-silica nanocomposite materials fabricated with the help of THEOS. Their formation, properties and structure as well as features and possible mechanism for the sol-gel processes are considered. It is demonstrated that the novel approach is particularly suitable in situations where others are unsatisfactory. This includes systems of which supramolecular organization or phase state is sensitive to the pH of solutions, temperature and addition of organic solvents. One example of a successful application is the immobilization of labile enzymes. The biocompatibility of THEOS allows their activity to be retained, thereby enhancing long-term and thermal stabilities.     

Plasmonic-enhanced two-photon fluorescence with single gold nanoshell

Single gold nanoshell with mutilpolar plasmon resonances is proposed to enhance two-photon fluorescence efficiently.The single emitter single nanoshell configuration is studied systematically by employing the finite-difference time-domain method.The emitter located inside or outside the nanoshell at various positions leads to a significantly different enhancement effect.The fluorescent emitter placed outside the nanoshell can achieve large fluorescence intensity given that both the position and orientation of the emission dipole are optimally controlled.In contrast,for the case of the emitter placed inside the nanoshell,it can experience substantial two-photon fluorescence enhancement without strict requirements upon the position and dipole orientations.Metallic nanoshell encapsulating many fluorescent emitters should be a promising nanocomposite configuration for bright two-photon fluorescence label.The results provide a comprehensive understanding about the plasmonic-enhanced two-photon fluorescence behaviors,and the nanocomposite configuration has great potential for optical detecting,imaging and sensing in biological applications.     

Disodium terephthalate/multiwall-carbon nanotube nanocomposite as advanced anode material for Li-ion batteries

Organic small molecule materials have attracted extensive attention due to their environmentally friendly, sustainability, and low cost which can be obtained from biomass and recyclable resources for Li/Na-ion batteries. However, the intrinsic poor electronic conductivities and the dissolution in organic liquid electrolyte lead to poor electrochemical performance, thus preventing them from practical application. To tackle these issues, herein, we take disodium terephthalate (Na₂TP) as an example and report an organic/multiwall-carbon nanotube nanocomposite via a simple spray drying methodology as an anode material for Li-ion battery. It delivers improved electrochemical performance compared to the pristine Na₂TP microspheres produced by the same spray drying method and the bulk microsized Na₂TP prepared by a conventional water-crystallization method. This is mainly due to the as-prepared nanocomposite can shorten the Li-ion diffusion distance, form highly conductive network and slow the dissolution rate. Our simple methodology could be of interest designing newly organic composites.     

Controlling cell-material interactions with polymer nanocomposites by use of surface modifying additives

Polymer nanocomposites (NC) are fabricated by incorporating well dispersed nanoscale particles within a polymer matrix. This study focuses on elastomeric polyurethane (PU) based nanocomposites, containing organically modified silicates (OMS), as bioactive materials. Nanocomposites incorporating chlorhexidine diacetate as an organic modifier (OM) were demonstrated to be antibacterial with a dose dependence related to both the silicate loading and the loading of OM. When the non-antibacterial OM dodecylamine was used, both cell and platelet adhesion were decreased on the nanocomposite surface. These results suggest that OM is released from the polymer and can impact on cell behaviour at the interface. Nanocomposites have potential use as bioactive materials in a range of biomedical applications.     

超微镍粒子/聚苯胺纳米复合材料制备及其表征

反相微乳液法 (inversemicroemulsionsystems ,W /O型 )是制备纳米复合材料有效而简单的液相化学制备方法[1,2 ] .本工作首次采用两步连续反相微乳液法原位聚合制备超微镍粒子 (Ni) /聚苯胺 (PANI)纳米复合材料 .首先 ,利用无机化合物之间的氧化还原反应 ,将十二烷基苯磺酸钠 (DBS)和NiCl2 溶液按一定比例加入锥形瓶中 ,再加入异戊醇和正庚烷混合溶剂 ,常温下电磁力搅拌 ,体系变得半透明 (淡黄色 )形成微乳溶液 (W /O型 )称为 (A) ;然后再配制DBS和NaBH4 与异戊醇和正庚烷混合溶剂 ,形成微乳溶液 (W /O型 )称为 (B) ;两步连续反相…     

Organic nanocrystals grown in sol–gel matrices: a new type of hybrid material for optics

We have engineered new hybrid organic–inorganic materials through a simple and generic preparation of stable organic nanocrystals grown in gel–glass matrices. This process is based on the confined nucleation and growth of dyes in the pores of dense gels. For bulk samples, narrow size distributions of particles are obtained between 10 and 20 nm in diameter. We have extended this method to the preparation of organic nanocrystals embedded in sol–gel thin films by spin-coating. For all these nanocomposite samples, we have significantly increased the stability of the dye and obtained promising linear and nonlinear optical properties. To cite this article: J. Zaccaro et al., C. R. Physique 3 (2002) 463–478.     

褐煤添加对羊粪有机肥发酵过程中水溶性有机物光谱学变化特征的影响

研究添加褐煤对羊粪有机肥中水溶性有机物(DOM)光谱学特性的影响,为高腐殖酸有机肥的腐熟度评价提供依据。以内蒙古褐煤、羊粪为原料,添加10%褐煤进行羊粪有机肥发酵,对不同阶段有机肥样品的DOM进行紫外可见光谱、荧光光谱、FTIR的表征。紫外-可见吸收光谱分析显示,有机肥样品的E₄/E₆值随着有机肥发酵的进行呈现出先下降后上升的趋势,由有机肥开始时的9.110 4降至最低为4.647 7,再升为有机肥结束时的5.390 1;A₁呈现先减小后增大趋势,A₂和A₃均呈现先增大后减少的趋势,峰值出现在12 d。同步荧光光谱显示,荧光峰光强的比值(I₄₇₀/I₄₃₅) 由有机肥起始的0.452 8上升至有机肥结束的0.655 2;A_HLR/A_FLR呈现上升趋势,从有机肥开始的0.673 9上升至有机肥结束的1.040 8。经过18 d的有机肥发酵后,有机肥发酵结束后样品荧光强度小于有机肥起始时的荧光强度,而且10%褐煤添加的羊粪有机肥的相对荧光强度明显高于未添加褐煤的荧光强度。FTIR显示,18 d的有机肥发酵过程中DOM中的碳水化合物、蛋白质被逐渐分解,而羧基、含苯环的物质含量明显增加。随着发酵的进行,DOM中的非腐殖质物质转化为类腐殖质,不饱和结构的多聚化或联合程度变大,稳定度增加;添加褐煤可以有效促进羊粪中木质素类物质的分解,提高羊粪有机肥DOM的芳构化程度,促进羊粪有机肥腐熟。     

Synthesis and silica coating of calcia-doped ceria/mica nanocomposite by seeded polymerization technique

Calcia-doped ceria is of potential interest as an ultraviolet (UV) radiation blocking material in personal care products because of the excellent UV light absorption property and low catalytic ability for the oxidation of organic materials superior to undoped ceria. In order to reduce the oxidation catalytic activity further, calcia-doped ceria was coated with amorphous silica by means of seeded polymerization technique. Generally, nanoparticles of inorganic materials do not provide a good coverage for human skin because of the agglomeration of the particles. The platy particles are required to enhance the covering ability of inorganic materials. This can be accomplished by synthesis of calcia-doped ceria/mica nanocomposite with subsequent silica coating to control catalytic activity of calcia-doped ceria. Calcia-doped ceria/mica nanocomposite was prepared by soft solution chemical method followed by silica coating via seeded polymerization technique. Silica coated calcia-doped ceria/mica nanocomposite was characterized by X-ray diffraction, SEM, TEM, XPS and FT-IR.     

Effect of modifiers on mechanical properties of polymer-based composite materials

In this paper, we present the experimental results on the study of mechanical properties of polymer-based nanocomposite materials with carbon nanotube or ultradisperse diamond inclusions. Tests are performed by nanoindentation methods. The results obtained for nanocomposites and a polymer used as a matrix in nanocomposites are compared.     

Use of Time-Resolved Fluorescence Analysis to Assess Molecular Mobility and Ionic Conductivity in Nanocomposite Organic-Inorganic Gels

This work is a short review of studies on nanocomposite organic-inorganic gels by stretched-exponential analysis of fluorescence decay profiles. Emphasis is given to the conditions which allow maximum probe mobility and minimum confinement conditions with the aim to assess ionic conductivity in these materials and with the purpose to employ them with dye-sensitized photoelectrochemical solar cells and other analogous systems.     

超声化学法制备纳米WO3掺杂聚苯乙烯及其表征

 为了满足惯性约束聚变和电磁内爆实验对靶材料的需求，以W(CO)_{5/sub>为原料，利用超声化学法在线制备纳米WO3/sub>掺杂聚苯乙烯。所得样品用TEM，XPS，FTIR和TG进行了表征。测试结果表明，钨元素主要以WO3/sub>的形态存在，WO3/sub>粒径分布为20~50 nm，WO3/sub>微粒被聚苯乙烯完全包覆，掺杂后聚苯乙烯的热稳定性提高了70 ℃。在此基础上，对超声化学法的反应机理进行了探讨。研究表明：纳米WO3/sub>与聚苯乙烯分子链有一定的化学键结合，纳米WO3/sub>在聚苯乙烯基体中分布均匀。}     

Synthesis and photochemical properties of zinc–aluminum layered double hydroxide/organic UV ray absorbing molecule/silica nanocomposites

Organic ultraviolet (UV) ray absorbents have been used as sunscreen materials, but may pose a safety problem when used at high concentration. In order to prevent direct contact of organic UV ray absorbent to the human skin several organic UV absorbents such as 4-hydroxy-3-methoxybenzoic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 4-hydroxy-3-methoxycinnamic acid, 4,4′-diaminostilbene-2,2′-disulfonic acid, p-aminobenzoic acid and urocanic acid were intercalated into Zn₂Al layered double hydroxides (Zn₂Al-LDHs) by anion-exchange and/or co-precipitation reaction. Thereafter, the obtained nanocomposites were coated with amorphous silica. Significant amounts (20–40 mass%) of organic UV absorbers were intercalated as univalent and/or divalent anions. The UV ray absorption ability of the organic UV absorbents increased and their catalytic activity for the air oxidation of castor oil greatly decreased when they were intercalated into the interlayer spaces of the Zn₂Al-LDHs. The deintercalation of organic molecules from LDHs by the anion exchange reaction with carbonate ion could be greatly depressed by coating the nanocomposite powder with amorphous silica.     

Chemometric Analysis of Excitation Emission Matrices of Fluorescent Nanocomposites

The performance of multivariate curve resolution (MCR-ALS) to decompose sets of excitation emission matrices of fluorescence (EEM) of nanocomposite materials used as analytical sensors was assessed. The two fluorescent nanocomposite materials were: NH₂-polyethylene glycol (PEG200) functionalized carbon dots, sensible to aqueous Hg(II) (CD); and, CdS quantum dots attached to the dendrimer DAB, sensible to the ionic strength of the aqueous medium (CdS-DAB). The structures of these sets of EEM, obtained as function of the Hg(II) concentration and ionic strength, are characterized by collinear properties (CD) and non-linear spectral variations (CdS-DAB). MCR-ALS was able to detect that the source of the collinearities is the presence of different size CD that show similar affinity towards Hg(II). Moreover, MCR-ALS was able to model the non-linear spectral variations of the CdS-DAB that are induced by varying ionic strength. The chemometric pre-processing of the fluorescent data sets using soft-modelling multivariate curve resolution like MCR-ALS is a critical step to transform these nanocomposites with interesting fluorescent proprieties into analytical useful nanosensors.     

过渡金属Co2+离子掺杂ZnS硫化物纳米晶制备与中红外发光特性研究

利用不含有机相的简单水热法制备了Co^2+∶ZnS纳米晶,纳米晶具有立方闪锌矿结构,平均晶粒尺寸约为8.3 nm,在808 nm激光泵浦下具有2~5μm波段的中红外荧光发射,中心波长位于3400 nm和4700 nm,分别对应Co^2+离子的4T2(F)→4 A 1(F)和4T1(F)→4T2(F)的能级跃迁.进一步将制备的纳米晶在还原气氛下进行800℃热处理,获得立方闪锌矿和纤锌矿混合晶型的纳米晶,平均晶粒尺寸增大到22.5 nm左右,热处理后的纳米晶表面羟基含量更低,中红外荧光发射强度显著提高.该Co^2+∶ZnS纳米晶的制备方法简单、在制备过程中不引入有机相等荧光淬灭中心,同时证明通过后热处理过程可以进一步减少表面缺陷及羟基含量,使荧光强度得到大幅提升.     

Fabrication of oxide base nanostructures using pulsed laser ablation in aqueous solutions

Nanoparticles of TiO₂ and SnO₂ were obtained by laser ablation of Ti and Sn targets in both deionized water and sodium dodecyl sulfate (SDS) solutions. The crystallinity of the nanoparticles strongly depended on the SDS concentration in the solution. Well-crystallized oxide nanoparticles were most abundantly fabricated in SDS solution with around the critical micelle concentration. An inorganic/organic layered nanocomposite consisting of a zinc hydroxide layer and a SDS lamellar interlayer was obtained by the ablation of Zn in SDS solutions. The oxide and/or hydroxide can be formed by the rapid reactive quenching with water in the liquid–plasma interface, where ablated species can be oxidized by aqueous oxidation. The surfactant in the liquid medium could affect the aggregation and growth of nuclei after the oxidation. The preparation of Pt/TiO₂ nanocomposite particles by PLA of the bi-combinant target of Pt and TiO₂ is also reported. PACS 81.16.Mk; 81.10.Dn; 81.07.Bc     

分子间相互作用对有机分子发光性质的影响

有机固态发光材料因其在显示器、激光和光通信等领域的应用前景而受到越来越多的关注. 与单分子相比,有机固态中存在各种弱分子间相互作用,这些相互作用有时会对激发态性质和能量耗散途径产生较大的影响,从而产生较强的荧光或磷光. 因此揭示有机固态发光的内在机制是非常必要的. 本综述通过总结从单分子到聚集态激发态的几何结构、电子结构、电子振动耦合和能量耗散动力学的变化,简要概括了分子间相互作用如何诱导有机固体产生强荧光、热激活延迟荧光和室温磷光. 本综述希望能帮助深入理解有机固体的激发态特性,从而为设计优秀的固态发光材料提供思路.     

Carbon nanotubes/fluorinated polymers nanocomposite thin films for electrical contacts lubrication

The need to operate in extreme environmental conditions (ultra high vacuum, high temperatures, aerospatial environment, …) and the miniaturization toward micro electromechanical systems is demanding new materials in the field of low-level electrical contacts lubrication. Dry and chemically immobilized lubrication is expected to be an alternative to the traditional wet lubricants oils.With the goal to conciliate electrical conductivity and lubricant properties we designed nanocomposite thin films composed of a 2D carbon nanotubes network embedded in an organic matrix. The nanotubes networks were deposited on gold surfaces modified by electrochemical cathodic grafting of poly(acrylonitrile). The same substrate served for covalently bonding the low-friction organic matrix. Three different matrixes were tested: a perfluorinated oligomer chemically grafted and two different polyfluorinated acrylates electrochemically grafted. The nanocomposite thin films have been characterized by ATR FT-IR, XPS and Raman spectroscopy.We measured the effects of the different matrixes and the nanotubes addition on the tribological properties and on the contact resistances of the films.     

Organic–inorganic polymer hybrids prepared by the sol-gel method

This review focuses on some aspects of organic-inorganic hybrid materials prepared by the sol-gel method. This field has been studied worldwide as one of the nanotechnologies, and is now of current interest for both organic and inorganic scientists. The elaboration of organic–inorganic polymer hybrid materials using the sol-gel process can be accomplished by various approaches. The simplest method is increasing the compatibility by using physical interactions, covalent bonding and compatibilizer between organic polymer and silica gel. Other novel approaches, such as an in-situ method, NHSG (Non- Hydrolysis Sol-Gel) process, and use of reactive polymer hybrids resulted in the preparation of novel transparent organic–inorganic polymer hybrid materials. Stimulus responsive polymer hybrids are also mentioned. Furthermore, nano-structured organic–inorganic polymer hybrids are created by using supermolecular and self-assembly of organic molecules or polymers recently. The obtained nano-structured hybrid materials showed unique properties that could not be found in amorphous hybrid materials. The possibilities and applications of organic–inorganic polymer hybrid materials are also described in this review.