Creative Synthesis of Organic–Inorganic Molecular Hybrid Materials

Gon, Masayuki; Tanaka, Kazuo; Chujo, Yoshiki

doi:10.1246/bcsj.20170005

Cited by 86 publications

(34 citation statements)

References 148 publications

(58 reference statements)

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“…The same result was observed when a replicate was analyzed for both sample types. This confirms that the origin of the peculiar properties of studied hybrid material, revealed by other analytical techniques, cannot be explained by a different arrangement of the siloxane network, since most of silicon atoms appear to have been fully involved in the condensation reactions (2) and (3).…”

Section: Nuclear Magnetic Resonancesupporting

confidence: 76%

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Effects of post cure treatment in the glass transformation range on the structure and fire behavior of in situ generated silica/epoxy hybrids

Bifulco

Tescione

Capasso

et al. 2018

J Sol-Gel Sci Technol

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Effects of post cure treatment in the glass transformation range on the structure and fire behavior of in situ generated silica/epoxy hybrids Abstract A new "in situ" sol-gel synthesis procedure was exploited to produce silica/epoxy nanocomposites with 6 wt.% maximum silica content. 3-Aminopropyltriethoxysilane (APTS) was used as a coupling agent. The experimental results (fouriertransform infrared spectroscopy, FTIR, small-angle X-ray scattering, SAXS, transmission electron microscopy, TEM, nuclear magnetic resonance, NMR, and dynamic mechanical analysis, DMA) support that the structure consists of nanosized silica particles (maximum 1.25 nm in size) embedded in a hybrid co-continuous network. A post cure non-isothermal heating from 15 to 100°C (beyond the Tg of the neat epoxy) caused Tg and storage modulus to increase. The fire behavior, that, owing to severe regulations (i.e., in aerospace engineering), often prevents composites applications, was also studied. The formed silica domains prevented melt dripping phenomena during vertical flame spread tests. Cone calorimetry tests showed a remarkable decrease of the heat release rate (HRR) for all the hybrid systems with respect to the neat cured resin, even at very low silica loadings (i.e., 2 wt.%). This decrease was much more pronounced for the hybrid structures that were not subjected to the post cure thermal treatment. The use of multiple structural investigation techniques allowed to choose among multiple hypothesis and conclude that nanoparticles clustering is the main reason of the effects of the post curing treatments. Graphical Abstract SAXS of the samples before (EPO) and after (EPO_t) post cure thermal treatment in the glass transformation range. Effect of the post cure on the glass transformation temperature (Tg) and heat release rate (HRR) Photos of samples EPO and EPO 2% Si after vertical flame spread tests Highlights• A hybrid co-continuous network embedding nanoparticles (maximum 1.25 nm in size) was obtained;• A post-cure was performed above the glass transformation temperature, T g , of neat epoxy;• The post cure makes T g , storage modulus and Heat Release Rate (HRR) to increase;• No dripping in flame test and up to 40% HRR reduction for only 2 wt.% silica content is observed;• The post cure effects depend on nanoparticles clustering in the glass transformation range.

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Section: Nuclear Magnetic Resonancesupporting

confidence: 76%

“…They require nano-level molecular design but are expected to have unique properties that are not simply the sum of those of the composite components: unprecedented materials may be created with the hybrid strategy [3]. Aerogels may be strengthened through proper organic-inorganic hybridization strategies [4].…”

Section: Introductionmentioning

confidence: 99%

Effects of post cure treatment in the glass transformation range on the structure and fire behavior of in situ generated silica/epoxy hybrids

Bifulco

Tescione

Capasso

et al. 2018

J Sol-Gel Sci Technol

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“…Nanoarchitectonics may be a good navigator for evolution from materials to life activities 117 as well as design and constructions of highly advanced bioactive functional materials systems. Not limited to bio-related systems, 452,453 the ways of materials construction by nanoarchitectonics would become nice guides for developments of functional systems in chemistry including synthesis of novel molecules, 454,455 fabrication and functionalization of low-dimensional materials, 456,457 and construction of hybrid materials, 458 and others.…”

Section: Resultsmentioning

confidence: 99%

Chemistry Can Make Strict and Fuzzy Controls for Bio-Systems: DNA Nanoarchitectonics and Cell-Macromolecular Nanoarchitectonics

Komiyama

Yoshimoto

Sisido

et al. 2017

Bulletin of the Chemical Society of Japan

280

131

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In this review, we introduce two kinds of bio-related nanoarchitectonics, DNA nanoarchitectonics and cellmacromolecular nanoarchitectonics, both of which are basically controlled by chemical strategies. The former DNA-based approach would represent the precise nature of the nanoarchitectonics based on the strict or "digital" molecular recognition between nucleic bases. This part includes functionalization of single DNAs by chemical means, modification of the main-chain or side-chain bases to achieve stronger DNA binding, DNA aptamers and DNAzymes. It also includes programmable assemblies of DNAs (DNA Origami) and their applications for delivery of drugs to target sites in vivo, sensing in vivo, and selective labeling of biomaterials in cells and in animals. In contrast to the digital molecular recognition between nucleic bases, cell membrane assemblies and their interaction with macromolecules are achieved through rather generic and "analog" interactions such as hydrophobic effects and electrostatic forces. This cell-macromolecular nanoarchitectonics is discussed in the latter part of this review. This part includes bottom-up and top-down approaches for constructing highly organized cell-architectures with macromolecules, for regulating cell adhesion pattern and their functions in twodimension, for generating three-dimensional cell architectures on micro-patterned surfaces, and for building synthetic/natural macromolecular modified hybrid biointerfaces.

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“…By mixing polymers and inorganic components at the nanoscale, organic-inorganic polymer hybrids can be obtained. 4 These materials commonly showed thermal stability and toughness that originated from the inorganic components, as well as the intrinsic characteristics of the polymers. Therefore, hybridization is a valid strategy for improving the robustness of conventional polymers.…”

Section: Poss Element-blocks For Realizing Designable Hybridsmentioning

confidence: 99%

Recent progress in the development of advanced element-block materials

Gon

Tanaka

Chujo

2017

Polym J

Self Cite

140

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An element-block is defined as a minimum functional unit composed of heteroatoms. The concept of 'element-block material' for designing advanced materials was proposed in 2015. In this review, the recent progress in material designs based on this concept is described. From our research, several element-blocks as representative examples are selected, and their roles in each material are explained. Initially, research on the development of 'designable hybrids' by employing polyhedral oligomeric silsesquioxane (POSS) is illustrated. Multiple functions of hybrids composed of modified POSS and the significant roles of POSS in bio-related polymeric materials for solving critical problems in conventional 19 F MR probes and for realizing new sensing technologies are demonstrated. Next, solid-state luminescent materials containing o-carborane and group 13 element-blocks are discussed. The materials' highly efficient emission in the solid state and their origins are explained. Furthermore, stimuliresponsive luminescent chromism is summarized. The sensing mechanisms and the application of these materials as sensors are presented in this study. In the last part, we mention optically active element-blocks containing chiral P-stereogenic phosphorus. In this review, the characteristics originating from each element-block are explained.

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Creative Synthesis of Organic–Inorganic Molecular Hybrid Materials

Cited by 86 publications

References 148 publications

Effects of post cure treatment in the glass transformation range on the structure and fire behavior of in situ generated silica/epoxy hybrids

Effects of post cure treatment in the glass transformation range on the structure and fire behavior of in situ generated silica/epoxy hybrids

Chemistry Can Make Strict and Fuzzy Controls for Bio-Systems: DNA Nanoarchitectonics and Cell-Macromolecular Nanoarchitectonics

Recent progress in the development of advanced element-block materials

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