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Journal ArticleDOI

The nature of the silica cage as reflected by spectral changes and enhanced photostability of trapped Rhodamine 6G

01 Nov 1984-The Journal of Physical Chemistry (American Chemical Society)-Vol. 88, Iss: 24, pp 5956-5959
TL;DR: Rhodamine 6G was embedded in a matrix of silica gel glass by the sol-to-gel technique as discussed by the authors, and its photostability and non-leachability were discussed in comparison with other solid environments, such as adsorption on powders and within porous glasses, thin films, and doping of plastic matrices.
Abstract: Rhodamine 6G was embedded in a matrix of silica gel glass by the sol to gel technique. The special features of an inorganic oxide glass as a carrier of an organic dye are discussed in comparison with other solid environments, such as adsorption on powders and within porous glasses, thin films, and doping of plastic matrices. Among the advantages mentioned are photostability of the glass matrix, trapping of the dye molecule, and its total isolation from undesired interactions with its neighboring dye molecules, impurities, and photodecomposition products; nonleachability of the dye; the ability to reach stable very high dye concentrations; reduction of translational, rotational, and vibrational degrees of freedom of the trapped dye; good transparency down to the UV. Embedding R6G in the silica glass enables one to reach high concentrations without undesirable dye aggregation. Stokes shift is larger in the glass than in water. Photostability of the dye is higher in the glass than in water. A remarkable front-face fluorescence stability is observed. These observations, and a critical review of the literature, are used to elucidate the nature of the silica glass cage: it is suggested that it is a hydroxylic polar environment, though somewhat less polar than water. The rigidity of the cage is discussed in terms of required reorientation of the environment around an excited state.
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2,877 citations

Journal ArticleDOI
TL;DR: In this article, the authors propose a vectorial chemistry approach for the generation of new generations of hybrid materials, which will open a land of promising applications in many areas: optics, electronics, ionics, mechanics, energy, environment, biology, medicine for example as membranes and separation devices, functional smart coatings, fuel and solar cells, catalysts, sensors, etc.
Abstract: Organic–inorganic hybrid materials do not represent only a creative alternative to design new materials and compounds for academic research, but their improved or unusual features allow the development of innovative industrial applications. Nowadays, most of the hybrid materials that have already entered the market are synthesised and processed by using conventional soft chemistry based routes developed in the eighties. These processes are based on: a) the copolymerisation of functional organosilanes, macromonomers, and metal alkoxides, b) the encapsulation of organic components within sol–gel derived silica or metallic oxides, c) the organic functionalisation of nanofillers, nanoclays or other compounds with lamellar structures, etc. The chemical strategies (self-assembly, nanobuilding block approaches, hybrid MOF (Metal Organic Frameworks), integrative synthesis, coupled processes, bio-inspired strategies, etc.) offered nowadays by academic research allow, through an intelligent tuned coding, the development of a new vectorial chemistry, able to direct the assembling of a large variety of structurally well defined nano-objects into complex hybrid architectures hierarchically organised in terms of structure and functions. Looking to the future, there is no doubt that these new generations of hybrid materials, born from the very fruitful activities in this research field, will open a land of promising applications in many areas: optics, electronics, ionics, mechanics, energy, environment, biology, medicine for example as membranes and separation devices, functional smart coatings, fuel and solar cells, catalysts, sensors, etc.

2,321 citations

Journal ArticleDOI
TL;DR: In this paper, the creation of UOFMN (unified organically functionalized mesoporous networks) materials incorporates concepts employed in the synthesis of MCM-41 mesoporus silicates, making use of a quaternary ammonium cationic surfactant and a double trialkoxysilyl precursor such as bis(triethoxyilyl)ethane (BTSE) or bis(Triethoxyslyl)ethylene (bTSEY).
Abstract: Mesoporous materials have been synthesized that are composed of hybrid frameworks in which inorganic and organic components have a fixed stoichiometry and are covalently bonded. The creation of UOFMN (unified organically functionalized mesoporous networks) materials incorporates concepts employed in the synthesis of MCM-41 mesoporous silicates, making use of a quaternary ammonium cationic surfactant and a double trialkoxysilyl precursor such as bis(triethoxysilyl)ethane (BTSE) or bis(triethoxysilyl)ethylene (BTSEY). The cetyltrimethylammonium (CTA+) surfactant is removed by extraction with acid, resulting in a high surface area porous organosilicate framework in which Si atoms are bridged by ethane (from BTSE) or ethylene (BTSEY) groups. The channels are wormlike and uniform in diameter. UOFMN materials are more hydrothermally stable than MCM-41 prepared under similar conditions and have thicker pore walls. Ethylene groups in products made with BTSEY can be brominated, the brominated product itself being ...

1,215 citations

Journal ArticleDOI
TL;DR: The description and discussion of the major applications of hybrid inorganic-organic (or biologic) materials are the major topic of this critical review.
Abstract: Today cross-cutting approaches, where molecular engineering and clever processing are synergistically coupled, allow the chemist to tailor complex hybrid systems of various shapes with perfect mastery at different size scales, composition, functionality, and morphology. Hybrid materials with organic–inorganic or bio–inorganic character represent not only a new field of basic research but also, via their remarkable new properties and multifunctional nature, hybrids offer prospects for many new applications in extremely diverse fields. The description and discussion of the major applications of hybrid inorganic–organic (or biologic) materials are the major topic of this critical review. Indeed, today the very large set of accessible hybrid materials span a wide spectrum of properties which yield the emergence of innovative industrial applications in various domains such as optics, micro-electronics, transportation, health, energy, housing, and the environment among others (526 references).

1,159 citations

Journal ArticleDOI
TL;DR: In this paper, the core integrity of inorganic nanobuilding blocks (NBBs) is preserved and the main synthetic procedures presented in the literature are reviewed and extended to nanoparticule-based hybrid networks.
Abstract: This article describes hybrid materials and systems in which the core integrity of inorganic nanobuilding blocks (NBBs) is preserved and reviews the main synthetic procedures presented in the literature. The relation between the NBB and the resulting hybrid networks is discussed for several striking examples: silicon and tin oxo clusters, polyoxometalates, and transition metal−oxo-based clusters. This approach is extended to nanoparticule-based hybrids. The chemical strategies offered by the coupling of soft chemistry processes and this approach based on functional NBBs allows, through an intelligent and tuned coding, to develop a new vectorial chemistry that is able to direct the assembly of a large variety of structurally well-defined clusters or nanoparticles into complex architectures.

1,124 citations

References
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Book
01 Jan 1975

327 citations

Book
01 Jan 1980
TL;DR: In this article, the authors discuss the potential of the Mossbauer Effect and its application to Nuclei Other than Iron in the field of NMR and the application of ESR Spectroscopy to Inorganic-Clay.
Abstract: 1. Mossbauer Spectroscopy.- 1-1. Introduction to the Mossbauer Effect.- 1-2. Basic Principles of Mossbauer Spectroscopy.- 1-3. Instrumentation and Experimental Procedures.- 1-4. Application of Mossbauer Spectroscopy to the Study of Silicate Minerals.- 1-5. The Study of Mineral Alteration Reactions.- 1-6. Iron Oxides and their Characterization in Soils.- 1-7. Critical Assessment of the Potential of Mossbauer Spectroscopy, and its Application to Nuclei Other than Iron.- References.- 2. Neutron Scattering Methods of Investigating Clay Systems.- 2-1. Introduction.- 2-2. Elementary Neutron Scattering Theory.- 2-3. Neutron Scattering Instrumentation and Methods.- 2-4. Applications of Neutron Spectroscopy to Studies of Clay Minerals.- Appendix 2-1. Macroscopic Cross Section for a Montmorillonite-Water System.- Appendix 2-2. Calculation of Incoherent Scattering Intensity Ratios for a Clay-Water System.- References.- 3. Introduction to X-ray Photoelectron Spectroscopy.- 3-1. Introduction.- 3-2. Trend of XPS Spectra.- 3-3. Instrumentation.- 3-4. Peak Position.- 3-5. Explored Depth.- 3-6. Peak Intensity.- 3-7. Overview of Methods of Characterization of Solids Based on X-ray, Electron and Ion Beams.- References.- 4. Application of X-ray Photoelectron Spectroscopy to the Study of Mineral Surface Chemistry.- 4-1. Uniqueness of XPS for the Investigation of Mineral Surface Phenomena - Probing Depth.- 4-2. Sample Handling Techniques.- 4-3. Analytical Applications.- 4-4. Electron Take-Off (Grazing) Angle Analysis Applications.- 4-5. Qualitative Bonding Investigations.- 4-6. Summary.- References.- 5. The Application of NMR to the Study of Clay Minerals.- 5-1. Introduction: Fundamentals of NMR.- 5-2. The Bloch Equations.- 5-3. Line Shape.- 5-4. Relaxation Mechanisms.- 5-5. Review of Some Problems: Order and Disorder in Adsorbed Water Molecules.- References.- 6. Distribution of Ions in the Octahedral Sheet of Micas.- 6-1. Introduction.- 6-2. Influence of the Fe2+ Ions.- 6-3. H+ Spectra of Phlogopites.- 6-4. H+ Spectra of Biotites.- 6-5. F? Spectra.- 6-6. Correlation with I.R. Results.- References.- 7. General Theory and Experimental Aspects of Electron Spin Resonance.- 7-1. Introduction.- 7-2. G-Factor Tensor.- 7-3. Hyperfine Interaction.- 7-4. Analysis of ESR Spectra.- 7-5. Fine Structure.- 7-6. Summary.- Appendix 7-1.- Appendix 7-2.- Appendix 7-3.- References.- 8. Applications of ESR Spectroscopy to Inorganic-Clay Systems.- 8-1. Introduction.- 8-2. Surface-Bound Metal Ions.- 8- 3. Framework Paramagnetic Centers.- References.- 9. Application of Spin Probes to ESR Studies of Organic-Clay Systems.- 9- 1. Nitroxide Spin Probes - Origin of the ESR Spectrum.- 9-2. Nitroxides in Low-Viscosity Media - Rapid Isotropic Motion.- 9-3. Nitroxides in High-Viscosity Media.- 9-4. Nitroxides Adsorbed on Clay Surfaces.- 9-5. Experimental Considerations in Using Nitroxide Spin Probes.- References.- 10. Applications of Photoacoustic Spectroscopy to the Study of Soils and Clay Minerals.- 10-1. Introduction.- 10-2. Instrumentation.- 10-3. Results.- 10-4. Conclusions.- References.

49 citations

Journal ArticleDOI
TL;DR: In this paper, the authors discuss the potential of the Mossbauer Effect and its application to Nuclei Other than Iron in the field of NMR and the application of ESR Spectroscopy to Inorganic-Clay.
Abstract: 1. Mossbauer Spectroscopy.- 1-1. Introduction to the Mossbauer Effect.- 1-2. Basic Principles of Mossbauer Spectroscopy.- 1-3. Instrumentation and Experimental Procedures.- 1-4. Application of Mossbauer Spectroscopy to the Study of Silicate Minerals.- 1-5. The Study of Mineral Alteration Reactions.- 1-6. Iron Oxides and their Characterization in Soils.- 1-7. Critical Assessment of the Potential of Mossbauer Spectroscopy, and its Application to Nuclei Other than Iron.- References.- 2. Neutron Scattering Methods of Investigating Clay Systems.- 2-1. Introduction.- 2-2. Elementary Neutron Scattering Theory.- 2-3. Neutron Scattering Instrumentation and Methods.- 2-4. Applications of Neutron Spectroscopy to Studies of Clay Minerals.- Appendix 2-1. Macroscopic Cross Section for a Montmorillonite-Water System.- Appendix 2-2. Calculation of Incoherent Scattering Intensity Ratios for a Clay-Water System.- References.- 3. Introduction to X-ray Photoelectron Spectroscopy.- 3-1. Introduction.- 3-2. Trend of XPS Spectra.- 3-3. Instrumentation.- 3-4. Peak Position.- 3-5. Explored Depth.- 3-6. Peak Intensity.- 3-7. Overview of Methods of Characterization of Solids Based on X-ray, Electron and Ion Beams.- References.- 4. Application of X-ray Photoelectron Spectroscopy to the Study of Mineral Surface Chemistry.- 4-1. Uniqueness of XPS for the Investigation of Mineral Surface Phenomena - Probing Depth.- 4-2. Sample Handling Techniques.- 4-3. Analytical Applications.- 4-4. Electron Take-Off (Grazing) Angle Analysis Applications.- 4-5. Qualitative Bonding Investigations.- 4-6. Summary.- References.- 5. The Application of NMR to the Study of Clay Minerals.- 5-1. Introduction: Fundamentals of NMR.- 5-2. The Bloch Equations.- 5-3. Line Shape.- 5-4. Relaxation Mechanisms.- 5-5. Review of Some Problems: Order and Disorder in Adsorbed Water Molecules.- References.- 6. Distribution of Ions in the Octahedral Sheet of Micas.- 6-1. Introduction.- 6-2. Influence of the Fe2+ Ions.- 6-3. H+ Spectra of Phlogopites.- 6-4. H+ Spectra of Biotites.- 6-5. F? Spectra.- 6-6. Correlation with I.R. Results.- References.- 7. General Theory and Experimental Aspects of Electron Spin Resonance.- 7-1. Introduction.- 7-2. G-Factor Tensor.- 7-3. Hyperfine Interaction.- 7-4. Analysis of ESR Spectra.- 7-5. Fine Structure.- 7-6. Summary.- Appendix 7-1.- Appendix 7-2.- Appendix 7-3.- References.- 8. Applications of ESR Spectroscopy to Inorganic-Clay Systems.- 8-1. Introduction.- 8-2. Surface-Bound Metal Ions.- 8- 3. Framework Paramagnetic Centers.- References.- 9. Application of Spin Probes to ESR Studies of Organic-Clay Systems.- 9- 1. Nitroxide Spin Probes - Origin of the ESR Spectrum.- 9-2. Nitroxides in Low-Viscosity Media - Rapid Isotropic Motion.- 9-3. Nitroxides in High-Viscosity Media.- 9-4. Nitroxides Adsorbed on Clay Surfaces.- 9-5. Experimental Considerations in Using Nitroxide Spin Probes.- References.- 10. Applications of Photoacoustic Spectroscopy to the Study of Soils and Clay Minerals.- 10-1. Introduction.- 10-2. Instrumentation.- 10-3. Results.- 10-4. Conclusions.- References.

47 citations