Organic/Inorganic bioactive materials Part II: in vitro bioactivity of Collagen-Calcium Phosphate Silicate/Wollastonite hybrids

In the present study, novel hybrid materials of Collagen (C) and Calcium Phosphate Silicate/Wollastonite (CPS/W) were synthesized. The CPS/W ceramic was prepared via polystep sol-gel method. The dissolution test of CPS/W ceramic was filled with TRIS-HCl buffer. FTIR depicts that hydroxyl carbonate apatite (OHCO₃HA) was observed after 3 days of immersion in TRIS-HCl buffer. Biohybrids of C-CPS/W were produced from diluted hydrochloric acid collagen type I and ceramic powder with different ratios of C and CPS/W equal to 25:75 and 75:25 wt.%. The synthesized hybrids were characterized by FTIR, XRD and SEM. FTIR depicts a “red shift” if amide I could be attributed to the fact that the collagen prefers to chelate Ca²⁺ from partial dissolution of CPS/W ceramic. The growth of B-type carbonate containing hydroxyapatite (B-CO₃HA) on the C-CPS/W hybrids soaked in 1.5SBF was observed. The negatively charged carboxylate groups from the collagen may be responsible for hydroxyapatite (HA) deposition. This fact was confirmed by the “red shift” of carboxylate groups of collagen in FTIR spectra. The formation of HA was observed by FTIR, XRD and SEM.     

Organic / inorganic bioactive materials Part I: Synthesis, structure and in vitro assessment of collagen/silicocarnotite biocoatings

The silicocarnotite, as an inorganic part of the coatings, has been synthesized using a polystep sol-gel method. The chemical composition of the prepared silicocarnotite sol is described as 58.12 CaO, 29.42 P₂O₅, 12.45 SiO₂ (wt%), where Ca/P+Si = 1,67. The acid soluble type I collagen, as an organic part of the obtained coatings, was mixed with silicocarnotite powder in a weight ratio of 25:75 and 75:25 weight ratio without cross-linkage. The acidity of the obtained mixture was readjust with 25% NH₄OH to pH = 9.0. The mixture was then dried at 37°C for 12 h. The growth of B-type carbonate containing hydroxyapatite (B-type CO₃HA) in which CO₃ ²⁺→PO₄ ³⁻ on the surface of collagen/silicocarnotite coatings soaked in 1.5 simulated body fluid (1.5 SBF) was observed. The nucleation of B-type CO₃HA was estimated on the obtained coatings after 3 days immersion in 1.5 SBF. The negatively charged carboxylate groups from the collagen surface may be responsible for the HA deposition. This was confirmed by the “red shift” of carboxylate groups of collagen molecules in the FTIR spectra. After soaking in 1.5 SBF, the morphology of prepared coatings and HA formation was observed by SEM.     

Organic/inorganic bioactive materials part IV: <Emphasis Type="Italic">In vitro</Emphasis> assessment of bioactivity of gelatin-calcium phosphate silicate/wollastonite hybrids

Biohybrids consisting of gelatin (G) and calcium phosphate silicate/wollastonite (CPS/W) have not been prepared so far. In this work our results are focused on the possibility of obtaining G-CPS/W bioactive hybrids in vitro. XRD, FTIR, SEM/EDS techniques were employed to characterize the synthesized hybrid materials. FTIR shows that before immersion in 1.5 SBF the “red shift” of COO- band for pure G is observed. The presence of this bond could be attributed to the formation of COO-Ca²⁺ via non-biomimetic route. After immersion in 1.5 SBF, FTIR shows the presence of A- and B-type carbonate containing hydroxyapatite (A/B-CO₃HA). ESD and FTIR show that small amount of calcite (CaCO₃) are present after in vitro test in 1.5 SBF for 3 days. XRD reveals that CO₃HA and small amounts of CaCO₃ can be detected after in vitro test. SEM results obtained for immersed samples show that hydroxyapatite (HA) particles fully covered the surface of the hybrids by a layer composed of spherulites. At higher magnification, very small elongated crystallites could be observed.      

无机/有机纳米复合材料的研究进展*

分析总结了聚合物基无机纳米复合材料的各种制备方法、性质及其应用, 并对今后的发展作了展望。     

Synthesis and characterization of europium-containing luminescent bioactive glasses and evaluation of in vitro bioactivity and cytotoxicity

Luminescent europium-containing bioactive glasses (EuBG) based on the 58 %SiO₂–33 %CaO–9 %P₂O₅ (in mass, %) system were synthesized using sol–gel technique by adding Eu₂O₃ in silica network. The structural, textural and optical properties, as well as in vitro bioactivity and biocompatibility of the material were characterized using various methods. The results show that all the Eu-containing bioactive glass materials exhibit an amorphous structure, large specific surface area, relatively uniform pore size distribution and high in vitro bioactivity, similar to the conventional sol–gel bioactive glass. More importantly, the addition of Eu₂O₃ endow the material with a luminescent property even after immersion in aqueous solution and the luminescent intensity increases with the increase of Eu₂O₃ content. The cytotoxicity assay indicates that pure EuBG extract significantly inhibit the growth of rat marrow mesenchymal stem cells (rMSCs), while 25 % concentration of the extract diluted by culture medium could significantly improve the proliferation of rMSCs in comparison with pure medium. According to the above results, the material presents excellent apatite-forming activity, luminescent property and biocompatibility, demonstrating their potential applications in the fields of bone regeneration and drug delivery system.     

有机及有机无机杂化太阳电池中的界面研究

第3代可溶液加工的太阳电池(包括有机太阳电池、钙钛矿太阳电池等),因为制备成本低、可制备柔性器件等特点备受关注.它们的迅速发展与活性层材料、界面材料与修饰以及器件工程等方面的快速发展息息相关,其中器件中的各个界面对激子的分离、载流子传递和收集有着巨大的影响,影响着器件的性能.本文重点介绍了近年来我们课题组在有机太阳电池、聚合物/量子点杂化太阳电池以及钙钛矿太阳电池研究中,如何设计界面材料以及通过自组装层对电极进行界面修饰,实现活性层和电极之间的欧姆接触和载流子的有效收集;如何在界面层中引入具有等离激元效应的纳米粒子实现光场的有效利用和性能的提升;以及如何对聚合物和纳米粒子间的界面修饰实现载流子的高效分离,制备高性能的杂化太阳电池器件.     

Transparent Organic/Inorganic Hybrid Gels: A Classification Scheme

An attempt is made to classify transparent organic/inorganic materials synthesized by the sol–gel process. The chemical structures of the hybrids are the main criteria for this classification. Three main types of organic/inorganic gels are distinguished and their basic physico-chemical characteristics are outlined. © 1997 by John Wiley & Sons, Ltd.     

Organic/Inorganic NLO materials based on reactive polyimides and a bulky alkoxysilane dye via sol/Gel process

A series of the organic–inorganic materials based on reactive polyimides and a bulky alkoxysilane dye (ASD) for second‐order nonlinear optics have been developed. Sol‐gel reaction of ASDs is utilized to grow a network in polymer matrices (composite) or to create inter‐polymer network among polyimide chains (hybrid). Moreover, a full interpenetrating polymer network (IPN) was formed through simultaneous free radical polymerization of a methacryloyl group containing polyimide, and sol‐gel process of ASDs. Scanning electron microscopy (SEM) results indicate that the inorganic networks are distributed uniformly throughout the polymer matrices on the molecular scale. The silica particle sizes are well under 1 µm based on AFM study. Second harmonic coefficients, d₃₃ of 4.5 to 48.5 pm/V have been obtained for the optically clear poled/cured polyimide/ASD samples. Excellent temporal stability was obtained for these NLO materials at 100 °C. The dynamic thermal and temporal stabilities of the IPN system were much better than those of composite and hybrid systems. Copyright ­© 2003 John Wiley & Sons, Ltd.     

Solid Acid-Base Control of Inorganic/Organic Hybrids by Inorganic Components for Molecule-Selectivity

Solid acid-base properties of methylsiloxane-based inorganic/organic hybrids were controlled by incorporation of inorganic components other than Si into methylsiloxane networks. The effect of different inorganic components on the solid acid-base properties was estimated by first-principles calculations based on density functional theory (DFT). The deprotonation tends to occur in the order Si < Al < Nb inorganic components, suggesting that the acidity increases in the same order. Methylsiloxane-based hybrids with solid acid-base properties were also synthesized by incorporating inorganic components derived from metal alkoxides. Hammett indicators revealed that the solid acidity increased in the order Si < Al < Nb inorganic components, which was consistent with the results of first-principles calculations. Preliminary experiments revealed that the methylsiloxane-based hybrids also provided a solid basic nature by containing Ca and Y inorganic components derived from metal alkoxides. The acidic hybrids were found to have Brønsted acid sites from the FT-IR experiments of adsorbed pyridine on the hybrids.     

Fluorescence Probing of Composite Organic/Inorganic Transparent Matrices

Transparent composite SiO2/organic matrices have been made by the sol-gel method using tetramethoxysilane and either cetyltrimethylammoniumbromide (CTAB) or a polyethylene glycol oligomer (PEG-200) or a cationic polyelectrolyte. We have investigated conditions under which transparent xerogel matrices are possible and we have characterized them mainly by time-resolved fluorescence probing using stretched exponentials. CTAB creates a hydrophobic and PEG-200 a hydrophilic subphase in the matrix. An important property of these composite matrices is that they allow molecular diffusion contrary to matrices made in the absence of surfactants or polymers.     

Preparation of CaCO3/Polystyrene Inorganic/Organic Composite Nanoparticles

CaCO₃/polystyrene inorganic/organic composite nanoparticles (50 nm) with a core/shell structure were synthesized in 80% yield by emulsion polymerization. Nanometer CaCO₃ was pretreated with γ‐methacryloxypropyltrimethoxysilane in order to introduce polymerizable groups onto its surface. Soxhlet extraction experiments have shown that only 4% of total encapsulating polystyrene (PS) was removable when the ratio of CaCO₃ to styrene was relatively low (14.8–29.6%), indicating strong adhesion between CaCO₃ and PS.     

Sol-gel bioactive glass-ceramics Part I: Calcium phosphate silicate/wollastonite glass-ceramics

In this work we present experimental results about synthesis, structure evolution and in vitro bioactivity of new calcium phosphate silicate/wollastonite (CPS/W) glass-ceramics. The samples obtained were synthesized via polystep sol-gel process with different Ca/P+Si molar ratio (R). The structure of the materials obtained was studied by XRD, FTIR spectroscopy and SEM. XRD showed the presence of Ca₁₅(PO₄)₂(SiO₄)₆, β-CaSiO₃ and α-CaSiO₃ for the sample with R=1.89 after thermal treatment at 1200°C/2h. The XRD results are in good agreement with FTIR analysis. SEM denotes that apatite formation can be observed after soaking in simulated body fluid (SBF).      

Organic derivatives of germanium : Part III. Synthesis of alkoxygermanes from organogermanium oxides

A number of alkoxides, glycollates, acetylacetonates and substituted amino derivatives of alkylgermanes have been prepared directly from their germoxanes for the first time. Molecular weights and refractive indices of these compounds have been determined.     

Novel carbazole/fluorene hybrids: host materials for blue phosphorescent OLEDs

[reaction: see text] A series of carbazole/fluorene (CBZm-Fn) hybrids were effectively synthesized through Friedel-Crafts-type substitution of the carbazole rings. These compounds were thermally and morphologically stable host materials for OLED applications. Efficient blue phosphorescent OLEDs were obtained when employing CBZ1-F2 as the host and FIrpic as the guest.     

Inorganic fluorinated materials in France: recent developments

The purpose of this very short review is obviously not to give an extensive image of the activities carried out in France these last years in various domains related to inorganic fluorine chemistry. At the turn of the century, it will rather focus on a few examples obtained in French research groups, mostly this last decade, in the fields of the synthesis and discovery of some outstanding chemical and physical properties of inorganic fluorinated materials.     

新型无机/有机复合柱撑粘土材料的合成与表征

以无机TiCl4／HCl制成的钛基柱撑液和十六烷基三甲基溴化胺(CTAB)为有机改性液,通过控制两种柱撑液的加入顺序以及相对含量,利用蒙脱石粘土矿物层间域的特殊化学反应场所的特性,合成得到三类复合柱撑蒙脱石材料．X射线衍射结果表明,d001晶面由于CTAB与钛基水合离子的相互作用形成粒度不同的柱撑空间而表现为两个峰值．与FT-IR光谱相比,FT-Raman光谱能够更加有效地表征和鉴定复合柱撑粘土的结构差别．采用原土无机柱撑后再有机柱撑,可以合成层间距更大的复合柱撑粘土材料．经热处理后得到锐钛型氧化钛的改性粘土材料,并且可以重新合成得到无机／有机复合柱撑的新型改性粘土材料．这些合成手段为制备新型改性粘土材料应用于环保以及化工等方面提供了借鉴．